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Metal halide perovskite nanocrystals (NCs), known for their strong visible-light absorption and tunable optoelectronic properties, show significant promise for photocatalytic applications. However, their efficiency is often hindered by rapid charge recombination and insufficient exciton dissociation, limiting effective catalysis. Excited-state interactions at the NC interface are critical in determining photocatalytic performance, underscoring the need for strategies that enhance charge separation and minimize recombination. To address these challenges, we developed a composite material by combining cesium lead bromide (CsPbBr 3 ) nanocrystals with ferrocene carboxylic acid (FcA), a hole-extracting moiety. This integration enhances exciton dissociation through energy level alignment and recombination suppression, resulting in a 3-fold increase in the photocatalytic oxidation yield of benzylamine to N -benzylidenebenzylamine (35 ± 5% versus 12 ± 2% for pristine CsPbBr 3 ). Additionally, thionyl bromide (SOBr 2 ) surface modification strips off ligands and introduces bromide ions onto the CsPbBr 3 NCs, further improving charge transfer and substrate accessibility, resulting in a 27 ± 5% yield within 3 h. While SOBr 2 treatment enhances initial catalytic performance, its acidic nature may lead to reversible reactions and side products over extended reaction times. This study highlights the impact of molecular integration and surface engineering on optimizing interfacial charge dynamics, providing a pathway toward robust, high-efficiency perovskite photocatalysts for sustainable chemical transformations.

Although photocatalytic disinfection can avoid secondary pollution and other shortcomings compared to traditional disinfection methods, its development is seriously hindered by poor charge separation and transfer efficiency. Herein, we design a Zn-NC (single Zn atoms embedded in nitrogen-doped carbon) bridged ZnO/C 3 N 4 Z-scheme heterojunction (ZnO/Zn-NC/C 3 N 4 ) with robust interface contact by a multi-interfacial engineering strategy to achieve highly efficient separation and transfer of charge. Experimental and theoretical analyses demonstrate that the tightly integrated interface and excellent electrical conductivity of Zn-NC electron bridges ensure effective transfer of photogenerated charge carriers. Compared to ZnO/C 3 N 4 , the introduction of Zn-NC electron bridges induces charge rearrangement at the interface, generating a strong built-in electric field in the ZnO/Zn-NC/C 3 N 4 Z-scheme heterojunction to facilitate the separation and transfer of photogenerated charge carriers. Furthermore, Zn-NC electron bridges effectively promote the adsorption and activation of oxygen on the surface of ZnO/Zn-NC/C 3 N 4 , enhancing the generation of reactive oxygen species for rapid bacteria elimination in water. Consequently, the ZnO/Zn-NC/C 3 N 4 Z-scheme heterojunction, at a concentration of 100 ppm, achieves 99.9 % antibacterial efficiency against methicillin-resistant Staphylococcus aureus, Staphylococcus aureus, and Escherichia coli at a bacterial concentration of ∼ 10 7 CFU/mL under AM 1.5G simulated sunlight irradiation for 60 min, which is approximately 1.05 times higher than that of ZnO/C 3 N 4 . Moreover, ZnO/Zn-NC/C 3 N 4 maintains a 99.9 % bactericidal efficiency for natural water treatment using a homemade microreactor, demonstrating its potential for water disinfection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

The magnetic field as a "non-contact" external field can instantaneously affect the separation and migration of photogenerated carriers during the photocatalytic reaction. This facilitates the large-scale industrial application of photocatalysis technology. Consequently, the potential for using external magnetic fields to enhance photocatalysis in environmental pollution control and clean energy production has received significant attention. Herein, the principle of the magnetic field acting on photocatalytic reaction is discussed, including spin polarization, the Lorentz force, negative magnetoresistance, and electromotive force. In particular, the typical reaction devices and magnetic field settings involved in current research on magnetic field-assisted photocatalysis are exhibited. Meanwhile, the performance of magnetic field-assisted photocatalysis in specific applications is presented. The efficiency and experimental parameters of catalysts are classified and organized by their specific application fields. It is highlighted to summarize and interpret the mechanisms underlying magnetic field-assisted photocatalysis presented in previous studies, along with the latest validation techniques. Finally, the challenges and potential opportunities are discussed. This review offers valuable insights and guidance for the design and development of innovative magnetic field-assisted photocatalytic systems, thereby accelerating the industrial application of photocatalytic technology., (© 2025 Wiley‐VCH GmbH.)

Tungsten trioxide (WO 3 ) suffers from the rapid recombination of photogenerated charge carriers. For practical photoelectrochemical (PEC) water splitting, effective oxygen evolution catalysts need to be introduced to alleviate electron-hole recombination. Prussian blue analogues, with their open framework structures and adjustable metal centers, have emerged as promising candidates for oxygen evolution catalysts. This study investigates the deposition of Cobalt hexacyanoferrate (CFP) nanoparticles with different iron valence states (III and II) on terrace-like WO 3 (TW) photoanodes via a simple sequential dipping method. Notably, CFP(III) has shown to exhibit a stronger influence on photocurrent response than CFP(II). Based on Mott-Schottky studies and density functional theory calculations, CFP(III) facilitates a reduction in the depletion layer width, improves photoinduced hole kinetics, and induces steeper band bending in CFP(III)-TW, thereby enhancing PEC performance. The CFP(III)-TW photoanode achieves a photocurrent density of 1.64 mA cm -2 at 1.23 V RHE under visible light, which is 2 times and 5.4 times higher than that of TW and porous WO 3 films, respectively. Photoinduced holes with longer lifetimes suggest CFP(III)-TW experiences less surface recombination and faster separation of charge carriers compared to that of TW and CFP(II)-TW. The scalability of the CFP(III)-TW is demonstrated through the fabrication of a 25 cm 2 sheet, attaining a current of 4.6 mA at 1.23 V RHE under visible light illumination. This study highlights the straightforward synthesis of low-cost, environmentally friendly photoanode materials and establishes CFP(III)-TW as a scalable and efficient oxygen evolution catalyst for practical PEC water splitting applications. These findings underscore the potential of CFP(III) as a promising material for advancing renewable energy technologies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier Inc. All rights reserved.)

Kinetic factors frequently emerge as the primary constraints in photocatalysis, exerting a critical influence on the efficacy of polymeric photocatalysts. The diverse conjugation systems within covalent organic frameworks (COFs) can significantly impact photon absorption, energy level structures, charge separation and migration kinetics. Consequently, these limitations often manifest as unsatisfactory kinetic behavior, which adversely affects the photocatalytic activity of COFs. To address these challenges, we propose a methoxy (-OMe) molecular engineering strategy designed to enhance charge carrier kinetics and mitigate mass transfer resistance. Through strategic modulation of the position and quantity of -OMe units, we can effectively manipulate the p-π conjugation, thereby enhancing charge separation and migration. Moreover, COFs enriched with -OMe moieties exhibit enhanced mass transfer dynamics due to the hydrophilic nature of methoxy groups, which facilitate the diffusion of reactants and products within the porous structure. This approach is hypothesized to drive an efficient photocatalytic hydrogen evolution reaction., (© 2024 Wiley-VCH GmbH.)

The efficiency of photoelectrochemical (PEC) water splitting is hindered by the slow kinetics of the oxygen evolution reaction (OER). This study developed a composite photoanode for water oxidation by incorporating ternary LDHs (ZnCoAl-LDH) onto Ti-Fe 2 O 3 as a cocatalyst. The ZnCoAl-LDH/Ti-Fe 2 O 3 photoanode achieved a photocurrent density of 3.51 mA/cm 2 at 1.23 V vs. RHE, which is 9.8 times higher than that of bare Ti-Fe 2 O 3 . Through a series of characterizations, the synergistic effects among the three metals were revealed. Furthermore, the addition of Zn can induce the formation of more high-valent Co, increasing the conductivity of CoAl-LDH and significantly reducing the surface charge transfer resistance. These advantages significantly enhance the injection efficiency of ZnCoAl-LDH/Ti-Fe 2 O 3 (82 %), thereby accelerating the OER kinetics of Ti-Fe 2 O 3 . Our work introduces new approaches for selecting photoelectrochemical cocatalysts and designing high-performance photoanodes for water splitting., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Plasmonic resonance intensity in metallic nanostructures plays a crucial role in charge generation and separation, directly affecting plasmon-induced photocatalytic activity. Engineering strategies to enhance plasmonic effects involve designing specific nanostructures, such as triangular nanoplates with sharp corners or dimer nanostructures with hot spots. However, these approaches often lead to a trade-off between enhanced plasmonic intensity and resonance energy, which ultimately determines local charge density and photocatalytic performance. Here, inspired by theoretical predications, it is shown that a flexibly controlled plasmonic photocatalyst, consisting of an ordered array of Au nanoparticles on a SrTiO 3 surface, exhibits an enhanced surface plasmon resonance (SPR) intensity while maintaining a constant SPR resonant energy, due to the presence of surface lattice resonance. This trade-off results in improved charge separation efficiency and an increase in local charge density at catalytically active sites, as verified by theoretical simulations, surface photovoltage microscopy, and ultrafast transient absorption spectroscopy. Moreover, the optimized periodic photocatalyst shows a 7-fold increase in water oxidation activity over disordered nanostructures. This work provides a novel approach for balancing the intensity and energy of SPR, which will contribute to optimizing photocatalytic activity on plasmonic platforms., (© 2024 Wiley‐VCH GmbH.)

Superlattice materials have emerged as promising candidates for water electrocatalysis due to their tunable crystal structures, electronic properties, and potential for interface engineering. However, the catalytic activity of transition metal-based superlattice materials for the hydrogen evolution reaction (HER) is often constrained by their intrinsic electronic band structures, which can limit charge carrier mobility and active site availability. Herein, a highly efficient electrocatalyst based on a VS 2 -VS heterodimensional (2D-1D) superlattice with sulfur vacancies is designed addressing the limitations posed by the intrinsic electronic structure. The enhanced catalytic performance of the VS 2 -VS superlattice is primarily attributed to the engineered heterojunction, where the work function difference between the VS 2 layer and VS chain induces a charge separation field that promotes efficient electron-hole separation. Introducing sulfur vacancies further amplifies this effect by inducing quantum localization of the separated electrons, thereby significantly boosting HER activity. Both theoretical and experimental results demonstrate that the superlattice achieves a ΔG H* of -0.06 eV and an impressively low overpotential of 46 mV at 10 mA·cm -2 in acidic media, surpassing the performance of commercial Pt/C while maintaining exceptional stability over 15 000 cycles. This work underscores the pivotal role of advanced material engineering in designing catalysts for sustainable energy applications., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Inorganic photochromic materials offer several advantages over organic compounds, including relatively inexpensive and higher thermal stability. However, tuning their color with the same component has remained a significant challenge. In this study, we demonstrate that the photochromic color of Cu-doped ZnS nanocrystals (NCs), which is initially pale yellow before light irradiation, can be tuned from gray to brown by adjusting the surface stoichiometry of Zn and S, which is controlled through the use of thiol and non-thiol ligands. Several experiments and quantum chemical calculations using model clusters revealed that the color change is determined by the distribution of Cu, which significantly contributes to the coloration, specifically whether it resides on the Zn-rich or S-rich surface. In contrast, particle size and Cu concentration were found to have little effect on the photochromic color. This study expands the diversity of photochromic responses in inorganic NCs and marks an important step toward the development of further advanced photochromic nanomaterials., (© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We prepared a series fully rigid spiro electron donor-acceptor orthogonal dyads, with closed form of rhodamine (Rho) as electron donor and naphthalene (Np)/anthraquinone (AQ) as electron acceptor, to access the long-lived triplet charge separation ( 3 CS) state, via the electron spin control method. We found strong dependency of the photophysical property of the dyads on the amino substitution positions of the Np chromophores in the dyads 1,8-DaNp-Rho and 2,3-DaNp-Rho. Nanosecond transient absorption (ns-TA) spectra show the population of the 3 LE state (lifetime: 47 μs) for 2,3-DaNp-Rho, however, long-lived 3 CS state was observed (τ CS =0.62 μs) for AQ-Rho, with a CS quantum yield of Φ CS =58 %. Based on femtosecond transient absorption (fs-TA) spectra, spin orbit charge transfer ISC (SOCT-ISC) is proposed to be responsible for the formation of the triplet states. Time-resolved electron paramagnetic resonance (TREPR) spectra of AQ-Rho indicate the presence of two states, a 3 LE state with zero field splitting (ZFS) D parameter of 1400 MHz and E parameter of -410 MHz, formed via radical pair ISC (RP-ISC) and SOCT-ISC mechanism; and a 3 CS state with the electron spin-spin interaction in the regime of spin-correlated radical pair (SCRP)., (© 2024 Wiley-VCH GmbH.)

The piezo-photocatalysis enhanced by piezoelectric nanogenerators is considered one of the most effective methods for treating emerging contaminants (ECs) in environmental water. In this study, BiFeO 3 /ZnIn 2 S 4 /Ag (BFO/ZIS/Ag) with boosting piezo-photocatalytic performance was synthesized by modulating the interaction between the step-scheme (S-scheme) heterojunction and the Mott-Schottky barrier. The catalytic rate of the optimized BFO/ZIS/Ag-0.01 catalyst is 4.85 × 10 -2 min -1 for the degradation of niazitidine (NZT) under both ultrasonic and visible light radiation, which is respectively 4.3 and 4.8 times higher than that of pure BFO and ZIS. Furthermore, the total organic carbon (TOC) test revealed that NZT degradation reached 98.4 % after 120 min of continuous reaction. This enhanced piezo-photocatalytic performance is mainly due to the synergistic effect of integrated heterojunction and piezoelectric field. DFT calculations revealed that the charge transfer enhancement at the heterogeneous interface resulted from directional electron transfer to ZIS via Zn-O and S-Ag channels, following the introduction of Ag nanoparticles, which shortened the carrier separation path. Additionally, BFO bent the band of the composite catalyst, promoting carrier separation. These resulted in the generation of abundant highly active 1 O 2 , which specifically targeted and disrupted stable NZT molecules. Moreover, BFO/ZIS/Ag-0.01 exhibited strong inhibitory and antibacterial effects against Escherichia coli and Staphylococcus aureus via electrostatic adsorption and ionization. This study offers new insights into the restoration of aquatic environments and bacterial disinfection through the use of piezoelectric catalytic materials., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025. Published by Elsevier Inc.)

Constructing heterojunctions between phase interfaces represents a crucial strategy for achieving excellent photocatalytic performance, but the absence of sufficient interface driving force and limited charge transfer pathway leads to unsatisfactory charge separation processes. Herein, a doping-engineering strategy is introduced to construct a In─N bond-bridged In 2 S 3 nanocluster modified S doped carbon nitride (CN) nanosheets Z-Scheme van der Waals (VDW) heterojunctions (In 2 S 3 /CNS) photocatalyst, and the preparation process just by one-step pyrolysis using the pre-coordination confinement method. Specifically, S atoms doping enhances the bond strength of In─N and forms high-quality interfacial In─N linkage which serves as the atomic-level interfacial "highway" for improving the interfacial electrons migration, decreasing the charge recombination probability. The detailed characterization results, along with theoretical calculations, confirm that both S atom incorporation and the formation of Z-Scheme VDW heterojunctions synergistically improve the internal electric field. This, in turn, accelerates charge separation and simultaneously enhances light absorption capacity. Consequently, the optimal hydrogen evolution performance of In₂S₃/CNS2 is 160.8 times greater than that of In₂S₃, 8.2 times higher than that of CNS. This study emphasizes the crucial role of atomic-scale interface regulation and intrinsic electric fields in Z-Scheme VDW heterojunctions, contributing to ameliorative photocatalytic performance., (© 2025 Wiley‐VCH GmbH.)

The judicious construction of interfaces with swift charge communication to enhance the utilization efficiency of photogenerated carriers is a viable strategy for boosting the photocatalytic performance of heterojunctions. Herein, an in-situ partial conversion strategy is reported for decorating lead-free halide perovskite Cs 3 Bi 2 Br 9 nanocrystals onto BiOBr hollow nanotube, resulting in the formation of an S-scheme heterojunction Cs 3 Bi 2 Br 9 /BiOBr. This unique in-situ growth approach imparts a closely contacted interface to the Cs 3 Bi 2 Br 9 /BiOBr heterojunction, facilitating interfacial electron transfer and spatial charge separation compared to a counterpart (Cs 3 Bi 2 Br 9 :BiOBr) fabricated via traditional electrostatic self-assembly. Additionally, the establishment of an S-scheme charge transfer pathway preserves the robust redox capability of photogenerated carriers. Furthermore, the free electron transfer from Cs 3 Bi 2 Br 9 to BiOBr promotes the activation of the NN bond and diminishes the energy barrier associated with the rate-determining step in the N 2 reduction process. Consequently, the Cs 3 Bi 2 Br 9 /BiOBr heterojunction exhibits highly selective photocatalytic N 2 reduction to NH 3 (nearly 100 %) at a rate of 130 μmol g -1  h -1 under simulated sunlight (100 mW cm -2 ), surpassing BiOBr, Cs 3 Bi 2 Br 9 , and Cs 3 Bi 2 Br 9 :BiOBr by factors of 6, 4, and 2, respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Designing efficient sulfide photocatalysts for the simultaneous split water into H 2 and O 2 continue to be an arduous challenge. Herein, a Zn-vacancy mediated S-scheme MnCdS/ZnS-V Zn heterojunction derived from MnCdS/MOF-5 via in-situ vulcanization of MOF-5 in a new-fashioned sacrificial reagent of Na 2 S/NaH 2 PO 2 was fabricated. The presence of Zn vacancy (V Zn ) was certified by TEM, XPS, EPR and PL results, which result in a new defect level in the band structure of ZnS. The S-scheme charge transfer path was established between MnCdS and ZnS-V Zn by V Zn vacancies, and the photocorrosion is depressed efficiently and a dramatic rise occurs on photocatalytic performance. The strong electron coupling effect of S-scheme heterojunction mechanism was confirmed via in-situ XPS, SPV, work function, and radicals test by EPR. The band gap and density of state about ZnS-V Zn and MnCdS are also calculated by the DFT. In HER semi-reaction, the strongest photocatalytic hydrogen generation rate of 20 % MnCdS/ZnS-V Zn is 394.4 μmol/h with a splendid apparent quantum efficiency of 16.43 % at 420 nm, and the turnover number (TON) is 98.6. The hydrogen production rate of 20 % MnCdS/ZnS-V Zn is drastically advanced by 123.25 times in contrast to the unadorned ZnS-V Zn . And superior photostability is also obtained. Prominently, the high-efficiency and steady photocatalytic overall water splitting rates of 5.7μmol/h (H 2 ) and 3.0μmol/h (O 2 ) were achieved over 20 % MnCdS/ZnS-V Zn with 1 %wt Pt and 5 %wt Co 3 O 4 nanorod as cocatalysts, and the photocatalytic stability was excellent. This research supplies neoteric insights for designing of highly efficient V Zn -mediated S-scheme sulfide photocatalysts to achieve pure water overall splitting with superior photocatalytic activity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Visible-light-driven photocatalytic hydrogen (H 2 ) production has been extensively studied as a clean and sustainable energy resource. Although sacrificial electron donors (SEDs) are commonly used to evaluate photocatalytic activity, their irreversible decomposition forces charge separation, which disrupts the inherent dual productivity of photocatalysis, that is, the formation of both the reduction and oxidation products. To achieve highly efficient photoinduced charge separation without SED decomposition, the layer-by-layer assembly of redox-active photosensitizing dyes and electron mediators through Zr 4+ -phosphonate bonds has been extensively studied as an artificial mimic of the electron transport chain in natural photosynthesis. This concept paper presents an overview of photoredox cascade catalytic (PRCC) systems comprising multiple Ru(II)-trisbipyridine-type dyes and mediator layers on Pt-loaded TiO 2 nanoparticles for H 2 production from redox reversible electron donors (RREDs). The PRCC structure-activity relationship for photocatalytic H 2 production is briefly discussed in terms of layer thickness, surface structure and modification, and cooperativity with molecular oxidation catalysts. Finally, new insights into the design of efficient dual-production photocatalysts based on the PRCC structure are presented., (© 2024 Wiley-VCH GmbH.)

[2]Rotaxanes offer unique opportunities for studying and modulating charge separation and energy transfer, because the mechanical bond allows the robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C 60 bis-adduct complex and two zinc porphyrin stoppers to address how the movable nanohoop affects light-induced charge separation and energy transfer between the rotaxane subcomponents. We found that neither the parent nanohoop [10]CPP nor its electron-deficient analogue aza[10]CPP actively participate in charge separation. In contrast, the nanohoops completely prevented through-space charge separation. This result is likely due to supramolecular "shielding", because charge separation was observed in the thread that acted as reference dyad. On the other hand, the suppression of electron transfer allowed the observation of energy transfer from the porphyrin triplet to the fullerene triplet state with a lifetime of ca. 25 μs. The presence of the interlocked nanohoops therefore leads to a dramatic switch between charge separation and energy transfer. We suggest that our results explain observations made by others in photovoltaic devices comprising nanohoops and may pave the way toward strategic uses of mechanically interlocked architectures in devices that feature (triplet) energy transfer., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long-lived charge-separated excitons. Installing cationic acridinium functionality in a pristine electron-rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor-acceptor dyad network that performed rapid and efficient oxidative Diels-Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of ≈4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra-stable charge-separated excitons of 1.9 nm diameter with no apparent radiative charge-recombination pathway, endorsing almost a million times better photo-response and catalysis than the state-of-the-art., (© 2024 Wiley‐VCH GmbH.)

Sb 2 Se 3 emerges as a promising material for solar energy conversion devices. Unfortunately, the common deep-level defect V Se (selenium vacancy) in Sb 2 Se 3 results in a low solar conversion efficiency. The post selenization process has been widely adopted for suppressing V Se . However, the effect of selenization on suppressing V Se is often compromised and even more V Se are induced due to defect-correlation. Herein, high-quality Sb 2 Se 3 films are prepared using an unconventional selenization process, with precisely regulating in situ annealing Se vapor pressure. It is found that moderate Se vapor pressure annealing can efficiently suppress V Se by overcoming defect-correlation, as well as promotes grain growth and forms a better heterojunction band alignment. Consequently, the Sb 2 Se 3 photocathode shows a high-level photocurrent of 19.5 mA cm -2 at 0 V RHE , an onset potential of 0.40 V RHE and a half-cell solar-to-hydrogen conversion efficiency of 1.9%, owing to the inhibited charge recombination, excellent charge transport and interface charge extraction. This work provides a significant insight to suppress deep-level defect V Se by adjusting Se vapor pressure for efficient Sb 2 Se 3 photocathode., (© 2024 Wiley‐VCH GmbH.)

This covers the roles of electrical forces in space, in creating planets, including the Earth and in creating the conditions on Earth that make life possible., (© 2025. The Author(s), under exclusive license to Springer Nature Switzerland AG.)

Element doping has been demonstrated as a useful strategy to regulate the band gap and electronic structure of photocatalyst for improving photocatalytic activity. Herein, ZnIn 2 S 4 (ZIS) nanosheets were doped with alkali metal ions (Li + , Na + or K + ) by a simple solution method. Experimental characterizations reveal that alkali metal ions doping reduce the band gap, raise the conduction band position, and improve surface hydrophilicity of ZIS. In addition, theoretical calculations show that Na doping increases the electron density at valence band maximum and surrounding S atom, which is conducive to produce more electrons and effective utilization of electrons, respectively. Benefited from above factors, Na-doped ZIS (Na-ZIS) shows the highest photocatalytic hydrogen evolution performance. Furthermore, CoSe 2 cocatalyst is loaded on the surface of Na-ZIS (CS/Na-ZIS), which further improve the charge separation and prolong the lifetime of charges. As a result, the optimized CS/Na-ZIS shows a H 2 evolution rate of 4525 μmol·g -1 ·h -1 with an apparent quantum efficiency of 27.5 % at 420 nm, which are much higher than that of pure ZIS. This study provides an in-depth understanding of the synergistic effect of Na doping and CoSe 2 cocatalyst in ameliorating photocatalytic activity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

It is essential for the development of highly efficient polymeric photocatalysts for hydrogen peroxide (H 2 O 2 ) production. Nevertheless, the non-uniform molecular structures and sluggish reaction pathway of polymeric photocatalysts lead to low conversion efficiency. In this work, we report sulfur-contained phenolic resins with regulated conjugation for photocatalytic H 2 O 2 production. Due to the substitution of sulfur for methylene in the phenolic resin structure, the conjugation degree of the material is adjusted, resulting in the formation of a built-in electric field. This effectively enhances the charge separation capability, enabling charge carriers to react faster with substrates. Through in situ characterization and theoretical calculations, we have unveiled that the introduction of sulfur can modulate the reaction pathway of phenolic resin materials, enabling a dual-pathway photocatalytic H 2 O 2 production mediated by non-radical species. Impressively, the sulfur-contained resin photocatalyst showcases exceptional H 2 O 2 production activity with a solar-to-chemical conversion efficiency of 1.4 % exceeding most reported systems, and generates 25 mmol m -2 of H 2 O 2 under natural sunlight through large-scale equipment. This work provides a facile strategy to separate the photogenerated electron-hole pairs of polymer photocatalysts to achieve efficient artificial photosynthesis., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Designing robust photocatalysts with broad light absorption, effective charge separation, and sufficient reactive sites is critical for achieving efficient solar energy conversion. However, realizing these aims simultaneously through a single material modulation approach poses a challenge. Here, a 2D ultrathin oxygen vacancy (Ov)-rich Bi 2 W 0.2 Mo 0.8 O 6 solid solution photocatalyst is designed and fabricated to tackle the dilemma through component and structure optimization. Specifically, the construction of a solid solution with ultrathin structure initially facilitates the separation of photoinduced electron-hole pairs, while the introduction of Ov strengthens such separation. In the meantime, the presence of Ov extends light absorption to the NIR region, triggering a photothermal effect that further enhances the charge separation and accelerates the redox reaction. As such, photoinduced charge carriers in the Ov-Bi 2 W 0.2 Mo 0.8 O 6 are separated step by step via the synergistic action of 2D solid solution, O V , and solar heating. Furthermore, the introduction of O V exposes surface metal sites that serve as reactive Lewis acid sites, promoting the adsorption and activation of toluene. Consequently, the designed Ov-Bi 2 W 0.2 Mo 0.8 O 6 reveals an enhanced photothermal catalytic toluene oxidation rate of 2445 µmol g -1  h -1 under a wide spectrum without extra heat input. The performance is 9.0 and 3.9 times that of Bi 2 WO 6 and Bi 2 MoO 6 nanosheets, respectively., (© 2024 Wiley‐VCH GmbH.)

Graphitic carbon nitride (gC 3 N 4 ) is an attractive photocatalyst for solar energy conversion due to its unique electronic structure and chemical stability. However, gC 3 N 4 generally suffers from insufficient light absorption and rapid compounding of photogenerated charges. The introduction of defects and atomic doping can optimize the electronic structure of gC 3 N 4 and improve the light absorption and carrier separation efficiency. Herein, the high efficiency of carbon nitride photocatalysis for hydrogen evolution in visible light is achieved by an S-modified double-deficient site strategy. Defect engineering forms abundant unsaturated sites and cyano (─C≡N), which promotes strong interlayer C─N bonding interactions and accelerates charge transport in gC 3 N 4 . S doping tunes the electronic structure of the semiconductors, and the formation of C─S─C bonds optimizes the electron-transfer paths of the C─N bonding, which enhances the absorption of visible light. Meanwhile,C≡N acts as an electron trap to capture photoexcited electrons, providing the active site for the reduction of H + to hydrogen. The photocatalytic hydrogen evolution efficiency of SDCN (1613.5 µmol g -1  h -1 ) is 31.5 times higher than that of pristine MCN (51.2 µmol g -1  h -1 ). The charge separation situation and charge transfer mechanism of the photocatalysts are investigated in detail by a combination of experimental and theoretical calculations., (© 2024 Wiley‐VCH GmbH.)

Separation of equally sized particles distinguished solely by material properties remains still a very challenging task. Here a simple separation of differently charged, thermo-responsive polymeric particles (for example microgels) but equal in size, via the combination of pressure-driven microfluidic flow and precise temperature control is proposed. The separation principle relies on forcing thermo-responsive microgels to undergo the volume phase transition during heating and therefore changing its size and correspondingly the change in drift along a pressure driven shear flow. Different thermo-responsive particle types such as different grades of ionizable groups inside the polymer matrix have different temperature regions of volume phase transition temperature (VPTT). This enables selective control of collapsed versus swollen microgels, and accordingly, this physical principle provides a simple method for fractioning a binary mixture with at least one thermo-responsive particle, which is achieved by elution times in the sense of particle chromatography. The concepts are visualized in experimental studies, with an intend to improve the purification strategy of the broad distribution of charged microgels into fractioning to more narrow distribution microgels distinguished solely by slight differences in net charge., (© 2024 The Author(s). Small Methods published by Wiley‐VCH GmbH.)

In this study, ZnO, CdS, ZnO/CdS, and ZnO/CdS/Co nanostructures were successfully synthesized using a simple chemical precipitation method. The formation of these nanostructures was confirmed through x-ray diffraction (XRD), but their morphological properties were analyzed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Their optical properties were investigated using UV-visible diffuse reflectance spectroscopy (UV-DRS) and photoluminescence spectroscopy (PL). The photocatalytic activity of these materials was tested for the degradation of Reactive Blue 160 (RB 160) under visible light. It was observed that ZnO/CdS nanocomposites exhibited superior photocatalytic performance compared to pure ZnO. Furthermore, the inclusion of cobalt (Co) in the ZnO/CdS nanocomposites significantly enhanced this activity, likely due to improved visible light absorption. These findings suggest that ZnO/CdS/Co nanocomposites are promising candidates for efficient photocatalytic applications, particularly in environmental remediation under visible light., (© 2024 John Wiley & Sons Ltd.)

Rapid charge recombination, limited light response, and slow surface reactions were observed in the photocatalysts, thereby limiting their future-oriented applications in photocatalytic hydrogen production through water splitting. Constructing a multi-channel charge separation photocatalysis system could solve those questions. In this study, Pd-TiO 2 -Cu 2 O composites were successfully accomplished via a facile chemical reduction method. The Pd-TiO 2 -Cu 2 O composite exhibited improved photocatalytic hydrogen production (13069.7 μmolg -1 h -1 ), which was over 6 times as much as that of pure TiO 2 . Based on the photo/electrochemical measurements, it was proposed that a Type II heterojunction was formed at the TiO 2 -Cu 2 O interface under light irradiation, and concurrently, a Schottky barrier was established between Pd and TiO 2 . Accordingly, the Type II heterojunction-created built-in electric field would facilitate the separation of photogenerated charges. Simultaneously, the introduction of Pd accelerates the accumulation of electrons and further enhances the charge transfer rate. The combination of such a Type II heterojunction and Schottky junction synergistically created a multi-channel charge separation system, optimizing surface reactions and thus improving photocatalytic efficiency. This work provided a rational approach for building efficient multi-component photocatalysis systems featuring Type II heterojunction/Schottky junction for photocatalytic hydrogen evolution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier Inc. All rights reserved.)

Doping with 3d transition metal atoms is a widely used strategy to enhance the photocatalytic activity of metal sulfides, although the introduction of d-electrons often leads to the formation of deep localized states that function as recombination centers, thereby reducing charge separation efficiency. In this study, cobalt (Co) dopants were introduced into CdIn 2 S 4 (CIS) nanosheets, and a combination of extensive characterization techniques and first-principles calculations was utilized to investigate their role in enhancing the photocatalytic hydrogen evolution reaction (HER). In the bulk structure of CIS, Co doping not only reduces the bandgap, improving visible light absorption without introducing deep localized levels but also increases the difference between the effective masses of electrons and holes, thus promoting carrier separation. At the surface, the electron-donating ability of Co is lower than that of the replaced In atoms, leading to modifications in the electronic properties of neighboring atoms. This results in optimized hydrogen adsorption free energy and enhanced HER kinetics. Consequently, the 3at%Co-CIS sample exhibits an optimal H 2 evolution rate of 0.83 mmol·g -1 ·h -1 under visible light, which is 3.95 times higher than that of pristine CIS. This work not only improves the photocatalytic performance of 2D CIS but also provides valuable insights into the role of transition metal doping in photocatalysts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025. Published by Elsevier Inc.)

The structural and electronic features of the stimuli-responsive supramolecular inter-ionic charge-transfer material containing electron accepting N -benzylyridinium-4-oxime cation (BPA4 + ) and electron donating hexacyanoferrate (II) are reported. The study of reversible stimuli-induced transformation between hydrated reddish-brown (BPA4) 4 [Fe(CN) 6 ]·10H 2 O and anhydrous blue (BPA4) 4 [Fe(CN) 6 ] revealed the origin of observed hydrochromic behavior. The comparison of the crystal structures of decahydrate and anhydrous phase showed that subsequent exclusion/inclusion of lattice water molecules induces structural relocation of one BPA4 + that alter the donor-to-acceptor charge-transfer states, resulting in chromotropism seen as reversible reddish-brown to blue color changes. The decreased donor-acceptor distance in (BPA4) 4 [Fe(CN) 6 ] enhanced charge-transfer interaction allowing charge separation via one-electron transfer, as evidenced by in-situ ESR and FTIR spectroscopies. The reversibility of hydrochromic behavior was demonstrated by in-situ HT-XRPD, hot-stage microscopic and in situ diffuse-reflectance spectroscopic analyses. The insight into electronic structural features was obtained with density functional theory calculations, employed to elucidate electronic structure for both compounds. The electrical properties of the phases during dehydration process were investigated by temperature-dependent impedance spectroscopy.

In photocatalysis, photogenerated charge separation is pivotal and can be achieved through various mechanisms. Building heterojunctions is a promising method to enhance charge separation, where effective contact and charge exchange between heterojunction components remains challenging. Mostly used synthesis processes for making heterostructures require high temperatures, difficult processes, or expensive materials. Herein, a heterojunction of potassium intercalated graphitic carbon nitride (K-CN) and nanoflakes of iron phosphor trisulfide (FPS) is designed via a simple mechanical grinding process to boost the hydrogen evolution by a factor of more than 25 compared to pure K-CN. This significant improvement is rarely reached by other combinations of two semiconductors without cocatalysts, such as platinum. It can be attributed to the band alignment and band bending of an S-scheme that is validated via optical and X-ray photoelectron spectroscopy. As a consequence, strong quenching of the photoluminescence and significant H 2 evolution occur for this unique heterojunction. Furthermore, the excellent durability of the designed photocatalytic heterostructure is confirmed by monitoring the catalysts' H 2 -evolution rate and crystal structure after 72 h under light illumination. This study opens up promising and simple pathways for constructing efficient S-scheme heterojunctions for photocatalytic water-splitting.

Highly efficient photocatalysts can be fabricated using favorable charge transfer nanocomposite channel structures. This study adopted pulsed laser ablation in liquid (PLAL) to obtain rGO-bridged TiO 2 /g-C 3 N 4 (rGO-TiO 2 /g-C 3 N 4 ) photocatalytic Z-scheme without the need for noble metals. In addition to evaluating the resulting nanocomposite (comprising rGO nanosheets, TiO 2 nanotubes, and g-C 3 N 4 nanosheets) CO 2 reduction effectiveness, its chemical, morphological, structural, and optical characteristics were examined using various analytical techniques. The findings revealed a synergistic interaction between g-C 3 N 4 and TiO 2 , suggesting the presence of unique interfacial bonding, as well as enhanced visible light absorption. Notably, the ternary rGO-TiO 2 /g-C 3 N 4 Z-scheme exhibits an excellent photocatalytic performance by photocatalytically converting CO 2 into CO and CH 4 , with 81 % selectivity towards the CO and 1.91 % apparent quantum efficiency at 420 nm. Thus, the findings can pave the way for various Z-scheme systems in wide photocatalytic applications., (© 2024 Wiley-VCH GmbH.)

Solar-energy-driven photocatalytic CO 2 reduction by H 2 O to high-valuable carbon-containing chemicals has become one of the greatest concerns in both scientific and industrial communities, due to its potential in solving energy and environmental problems. However, efficiency of photocatalytic CO 2 reduction by H 2 O is still far below the needs of large-scale applications. The reduction efficiency is closely related to ability of photocatalysts in absorbing visible light which is the main part of sunlight (44 %), separating photogenerated electron-hole pairs, adsorbing CO 2 and producing protons for reducing CO 2 . Thus, photocatalysts with enhanced visible light absorption, electron-hole separation, CO 2 adsorption and proton production are highly desired. Herein, we aim to provide a picture of recent progresses in improving ability of photocatalysts in visible light absorption, electron-hole separation, CO 2 adsorption and proton production, and give an outlook for future researches associated with photocatalytic CO 2 reduction by H 2 O., (© 2024 Wiley-VCH GmbH.)

Zn doped CuBi 2 O 4 photocathodes are prepared by using a low-cost solution-based spray pyrolysis method. The doping of Zn in CuBi 2 O 4 promotes the separation and migration of carriers and effectively increases the carrier density. Compared with CuBi 2 O 4 alone, the photoelectrochemical activity of the Zn doped CuBi 2 O 4 photoelectrode is improved with the photocurrent density of -0.56 mA/cm 2 at 0.4 V vs. RHE. This improvement is due to the lower electronegativity of Zn, which leads to the covalent increase of Cu-O and Bi-O bonds in CuBi 2 O 4 , which limits the recombination of photogenerated electrons and holes and improves charge separation and transport. This study presents an innovative approach to enhance the charge separation efficiencies of photocathodes by implementing element doping strategies, which may contribute to further research on photocatalytic water splitting., (© 2024 Wiley-VCH GmbH.)

Water pollution caused by dyes and industrial wastewater poses a significant threat to ecosystems. The purification of such pollutants presents a major challenge. Photocatalysis based on semiconductor materials is a potential wastewater treatment process due to its safety and cost-effectiveness. In the present work, Zn 1-2 x Ce x Dy x O (x = 0.01-0.05) semiconductors were prepared by the sol-gel auto-ignition method. The samples are denoted CDZO1, CDZO3, and CDZO5 for x  = 0.01-0.05, respectively. The X-ray diffraction and Raman spectroscopy results revealed the formation of ZnO hexagonal phase wurtzite structure for all synthesized compositions. Different structural properties were determined. It was found that the lattice parameters and the unit cell volume increased, while the crystallite size diminished as x varied from 0.01 to 0.05. Transmission electron microscopy observations confirmed the formation of nanoparticles with the desired chemical compositions. The specific surface area (SSA) values are found to be 39.95 m 2 /g, 48.62 m 2 /g, and 51.36 m 2 /g for CDZO1, CDZO5, and CDZO5 samples, respectively. The reflectance spectra were recorded to examine the optical properties of the different nanoparticles. The values of the optical band gap were 3.221, 3.225, and 3.239 eV for CDZO1, CDZO3, and CDZO5 samples, respectively. In addition, the photocatalytic performance towards RhB dye degradation for the different samples was assessed. It was established that the CDZO3 sample with a moderate SSA value exhibited the superior photocatalytic performance among the other as-prepared samples wherein the percentage of degradation efficiency, and kinetic constant rate attained their maximum values of 98.22 % and 0.0521 min -1 , respectively within 75 min. As per the obtained findings, it is evident that the Zn 1-2 x Ce x Dy x O photocatalyst has prominent potential for use in the degradation of dyes and offers a useful route for impeding the recombination of electron-hole pairs of zinc oxide material., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

While being important candidate for heterogeneous photocatalyst, conjugated polymer typically exhibits random charge transfers between the alternating donor and acceptor units, which severely limits its catalytic efficiency. Herein, inspired by natural photosystem, the concept of guiding the charge migration to specific reaction sites is employed to significantly boost photocatalytic performance of linear conjugated polymers (LCPs) with pendant functional groups via creating programmed charge-transfer channels from the backbone to its pendant moiety. The pendant benzothiadiazole, as revealed in both in situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations, can act as electron "reservoir" that aggregates electrons at the active sites. Moreover, the presence of charge-transfer channels, evidenced by transient absorption spectroscopy (TAS), accelerates the electron transfer, preventing the recombination of electrons and holes. As a result, in this elaborately-designed architecture, the photogenerated electron can move smoothly towards the reduction sites, facilitating the reduction of O 2 into H 2 O 2 , while remaining holes are directed to oxidation centers, simultaneously oxidizing furfuryl alcohol to furoic acid. The optimized photocatalyst LCP-BT demonstrates a competitive catalytic performance with H 2 O 2 productivity of 868.3 μmol L -1  h -1 (9.8 times higher than conventional random charge-transfer polymer LCP-1) and furfuryl alcohol conversion over 95 % after 6 h., (© 2024 Wiley-VCH GmbH.)

The development of artificial photocatalysts to convert CO 2 into renewable fuels and H 2 O into O 2 is a complex and crucial task in the field of photosynthesis research. The current challenge is to enhance photogenerated charge separation, as well as to increase the oxidation capability of materials. Herein, a molecular junction-type porphyrin-based crystalline photocatalyst (Ni-TCPP-TPyP) was successfully self-assembled by incorporating a nickel porphyrin complex as a reduction site and pyridyl porphyrin as an oxidation site via hydrogen bonding and π-π stacking interactions. The resulting material has a highly crystalline structure, and the formation of inherent molecular junctions can accelerate photogenerated charge separation and transport. Thus, Ni-TCPP-TPyP achieved an excellent CO production rate of 309.3 μmol g -1  h -1 (selectivity, ~100 %) without the use of any sacrificial agents, which is more than ten times greater than that of single-component photocatalyst (Ni-TCPP) and greater than that of the most organic photocatalysts. The structure-function relationship was investigated by femtosecond transient absorption spectroscopy and density functional theory calculations. Our work provides new insight for designing efficient artificial photocatalysts, paving the way for the development of clean and renewable fuels through the conversion of CO 2 using solar energy., (© 2024 Wiley-VCH GmbH.)

Despite the widespread use of titanium dioxide (TiO 2 ) in photocatalytic applications, its inherent limitations, such as low efficiency under visible light and rapid recombination of electron-hole pairs, hinder its effectiveness in environmental remediation. This study presents a comparative investigation of TiO 2 -based composites, including TiO 2 /ZrO 2 , ZnO, Ta 2 O 3 , SnO, Fe 2 O 3 , and CuO, aiming to assess their potential for enhancing photocatalytic applications. Photocatalysis holds promise in environmental remediation, water purification, and energy conversion, with TiO 2 being a prominent photocatalyst. To improve efficiency and broaden applicability, various metal oxide composites have been explored. Composites were synthesized and characterized using techniques such as XRD, SEM, TEM, and zeta potential analysis to evaluate their structural and morphological properties. Photocatalytic performance was assessed by degrading herbicide Imazapyr under UV illumination. Results revealed that, the photo-activity of all prepared composites were more effective than the photo-activity of commercial hombikat UV-100. The photonic-efficiency is arranged according to the order TiO 2 /CuO > TiO 2 /SnO > TiO 2 /ZnO > TiO 2 /Ta 2 O 3  > TiO 2 /ZrO 2  > TiO 2 /Fe 2 O 3  > Hombikat TiO 2 -UV100. All composites exhibited superior performance, attributed to enhanced light absorption and charge separation. The study underscores the potential of these composites for environmental remediation and energy conservation, offering valuable insights for the development of advanced photocatalysts., (© 2024. The Author(s).)

Harnessing waste heat from environmental or industrial sources presents a promising approach to eco-friendly and sustainable chemical synthesis. In this study, we introduce a thermoelectrocatalytic (TECatal) system capable of utilizing even small amounts of heat for hydrogen peroxide (H 2 O 2 ) production. We developed a nanohybrid structure, combining carbon nanotubes (CNTs) and Bi 2 Te 3 nanoflakes (Bi 2 Te 3 /CNTs), through a one-pot synthesis method. Bi 2 Te 3 , as a thermoelectric (TE) material, generates charge carriers under a temperature gradient via the Seebeck effect, enabling them to participate in surface redox reactions. However, the rapid recombination of these charge carriers greatly limits the TECatal activity. In the Bi 2 Te 3 /CNTs nanohybrid system, the introduction of CNTs substantially enhances the efficiency of H 2 O 2 production, as the strong bonding between CNTs and Bi 2 Te 3 , along with the excellent conductivity of CNTs, facilitates charge carrier separation and transport, as confirmed by TE electrochemical tests. This study underscores the significant potential of thermoelectric nanomaterials for converting waste heat into green chemical synthesis.

This study explores the optimal morphology of photochemical hydrogen evolution catalysts in a one-dimensional system. Systematic engineering of metal tips on precisely defined CdSe@CdS dot-in-rods is conducted to exert control over morphology, composition, and both factors. The outcome yields an optimized configuration, a Au-Pt core-shell structure with a rough Pt surface (Au@r-Pt), which exhibits a remarkable fivefold increase in quantum efficiency, reaching 86 % at 455 nm and superior hydrogen evolution rates under visible and AM1.5 G irradiation conditions with prolonged stability. Kinetic investigations using photoelectrochemical and time-resolved measurements demonstrate a greater extent and extended lifetime of the charge-separated state on the tips as well as rapid water reduction kinetics on high-energy surfaces. This approach sheds light on the critical role of cocatalysts in hybrid photocatalytic systems for achieving high performance., (© 2024 Wiley-VCH GmbH.)

Fundamental discoveries in electron transfer advance scientific and technological advancements. It is suggested that in plant and bacterial photosynthesis, the primary donor, a chlorophyll or bacteriochlorophyll dimer, forms an initial excited symmetry-breaking charge transfer state ( 1 CT*) upon photoexcitation that subsequently promotes sequential electron transfer (ET) events. This is unlike monomeric photosensitizer-bearing donor-acceptor dyads where ET occurs from the excited donor or acceptor ( 1 D* or 1 A*). In the present study, we successfully demonstrated the former photochemical event using an excited charge transfer molecule as a donor. Electron-deficient perylenediimide (PDI) is functionalized with three electron-rich piperidine entities at the bay positions, resulting in a far-red emitting CT molecule (D CT ). Further, this molecule is covalently linked to another PDI (A PDI ) carrying no substituents at the bay positions, resulting in wide-band capturing D CT -A PDI conjugates. Selective excitation of the CT band of D CT in these conjugates leads to an initial 1 D CT * that undergoes subsequent ET involving A PDI, resulting in D CT + charge separation product (k PDI - charge separation product (k CS ~10 9  s -1 ). Conversely, when A PDI was directly excited, ultrafast energy transfer (ENT) from 1 A PDI * to D CT (k ENT ~10 11  s -1 ) followed by ET from 1 D CT * to PDI is witnessed. While increasing solvent polarity improved k CS rates, for a given solvent, the magnitude of the k CS values was almost the same, irrespective of the excitation wavelengths. The present findings demonstrate ET from an initial CT state to an acceptor is key to understanding the intricate ET events in complex natural and bacterial photosynthetic systems possessing multiple redox- and photoactive entities., (© 2024 Wiley-VCH GmbH.)

With the increasing demand for effective methods to address environmental pollution, piezocatalysis has emerged as a promising approach for pollutant degradation under mechanical energy. However, the development of highly efficient piezocatalytic materials remains a challenge. This study aimed to increase the piezocatalytic activity of bismuth titanate (Bi 4 Ti 3 O 12 ) by modifying it with zinc stannate (ZnSnO 3 ) nanocubes. The composite catalysts were synthesized using a straightforward deposition and calcination process. The calcination process ensured the tight adhesion of ZnSnO 3 nanocubes to the Bi 4 Ti 3 O 12 surface, while facilitating strong interactions between ZnSnO 3 and Bi 4 Ti 3 O 12 , which enhanced electron transfer and heterojunction structure formation. Band structure analysis indicated that Bi 4 Ti 3 O 12 has higher conduction band and valence band potentials than ZnSnO 3 , forming a type-II heterojunction. Bi 4 Ti 3 O 12 possesses a higher Fermi level than ZnSnO 3 , resulting in interfacial electron drift and formation of a built-in electric field, which further promotes the directional transfer and separation efficiency of charge carriers within the composite catalyst. This hypothesis was confirmed by surface photovoltage spectroscopy, piezoelectric current response, and electrochemical analysis. Consequently, the ZnSnO 3 /Bi 4 Ti 3 O 12 composite exhibited significantly improved piezocatalytic performance in RhB degradation, achieving a degradation efficiency of 80 % within 90 min under ultrasonic vibration. The degradation rate of the optimal sample was 8.2 times that of Bi 4 Ti 3 O 12 and 6.3 times that of ZnSnO 3 . Additionally, experiments to detect reactive species were conducted to elucidate the mechanism behind the piezocatalytic RhB degradation. Holes and hydroxyl radicals were the main reactive species. This study may offer new insights into the design of efficient piezocatalytic materials., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Abundant defect-induced nonradiative recombination greatly reduces the charge separation efficiency in photocatalysts. Dielectric screening of defects has been proven to be an effective strategy to improve the charge separation efficiency; however, it has been rarely reported in photocatalysis. Here, a developed calcium poly(heptazine imide) (CaPHI) is utilized as a model photocatalyst to explore the dielectric screening of defects. Through embedding potassium ions in CaPHI, the dipole moment and polarity of the PHI structure are increased, thus enhancing the dielectric constant and enabling the dielectric screening of defects. In addition, compared to the original CaPHI, the optimized Ca/KPHI exhibits a 79.3% reduction in defect capture cross-section, and a decrease in the nonradiative recombination rate from 0.6224 to 0.1452 ns -1 , thus achieving an apparent quantum efficiency of 51.4% for H 2 production at 420 nm. This proposed dielectric screening strategy effectively addresses the issue of slow carrier transport and separation caused by defect-induced nonradiative recombination in photocatalysts.

Efficient charge separation is essential in various optoelectronic systems, yet it continues to pose substantial challenges. Building upon the recent evidence that chiral biomolecules can function as electron spin filters, this study aims to extend the application of chirality-driven charge separation from the molecular level to the mesoscale and supramolecular scale. Utilizing cellulose nanocrystals (CNCs) derived from cellulose, the most abundant biomaterial on Earth, this research leverages their self-assembly into chiral nematic structures and their dielectric properties. A device is introduced featuring a chiral nematic hybrid film composed of CNCs and quantum dots (QDs), decorated with iron oxide nanoparticles. Using the quantum-confined Stark effect (QCSE) to probe charge separation, we reveal significant sensitivity to the circular polarization of light and the chiral nematic structure of the film. This approach achieves effective, long-lasting charge separation, both locally and across length scales exceeding 1 μm, enabling potential applications such as self-assembled devices that combine photovoltaic cells with electric capacitance as well as optical electric-field hybrid biosensors.

The construction of nanostructured heterostructure is a potent strategy for achieving high-performance photoelectrochemical (PEC) water splitting. Among these, constructing BiVO 4 -based heterostructure stands out as a promising method for optimizing light-harvesting efficiency and reducing severe charge recombination. Herein, we present a novel approach to fabricate a type II heterostructure of core/shell Bi 2 S 3 /BiVO 4 using electrolytic deposition and successive ionic layer adsorption and reaction (SILAR) methods. We identify the type II heterostructure and the difference in fermi energy using UV-Vis spectroscopy, X-ray photoelectron spectroscopy, and PEC measurements. This redistribution of charges due to the fermi energy difference induces an interfacial built-in electric field from BiVO 4 to Bi 2 S 3 , reinforcing the photogenerated hole transfer kinetics from BiVO 4 to Bi 2 S 3 . The Bi 2 S 3 /BiVO 4 heterostructure exhibits a superior photocurrent (6.0 mA cm -2 ), enhanced charge separation efficiency (85 %), and higher open-circuit photovoltage (350 mV). Additionally, the heterostructure displays a prolonged average lifetime of charge (1.63 ns), verifying this heterojunction could boost interfacial carriers' migration via an additional nonradiative quenching pathway. Furthermore, the lower photoluminescence (PL) intensity demonstrates the interfacial built-in electric field is beneficial for boosting charge migration., (© 2024 Wiley-VCH GmbH.)

Photoelectrochemical (PEC) water splitting on semiconductor electrodes is considered to be one of the important ways to produce clean and sustainable hydrogen fuel, which is a great help in solving energy and environmental problems. Bismuth vanadate (BiVO 4 ) as a promising photoanode for photoelectrochemical water splitting still suffers from poor charge separation efficiency and photo-induced self-corrosion. Herein, we develop heterojunction-rich photoanodes composed of BiVO 4 and iron vanadate (FeVO 4 ), coated with nickel iron oxide (NiFeO x /FeVO 4 /BiVO 4 ). The formation of the interface between BiVO 4 and FeVO 4 (Bi-VO 4 -Fe bridges) enhances the interfacial interaction, resulting in improved performance. Meanwhile, high-conductivity FeVO 4 and NiFeO x oxygen evolution co-catalysts effectively enhance bulk electron/hole separation, interface water's kinetics and photostability. Concurrently, the optimized NiFeO x /FeVO 4 /BiVO 4 possesses a remarkable photocurrent density of 5.59 mA/cm 2 at 1.23 V versus reversible hydrogen electrode (vs RHE) under AM 1.5G (Air Mass 1.5 Global) simulated sunlight, accompanied by superior stability without any decreased of its photocurrent density after 14 h. This work not only reveals the crucial role of built-in electric field in BiVO 4 -based photoanode during PEC water splitting, but also provides a new guide to the design of efficient photoanode for PEC., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Photocatalytic H 2 production is envisioned as a promising pillar of sustainable energy conversion system to address the energy crisis and environmental issues but still challenging. Herein, a strategy is proposed to design a dual-metal cocatalysts consisting of Pt nanoclusters (Pt NCs) and In nanoparticles (In NPs) anchored on polymeric carbon nitride (Pt-In/CN) for boosting photocatalytic water splitting. As expected, the designed Pt-In/CN photocatalyst exhibits an impressive H 2 production rate of 6.49 mmol·h -1 ·g -1 with an apparent quantum yield (AQY) of 33.56 % at 400 nm, which is 2.8- and 11.2-fold higher than those of the Pt/CN and In/CN, respectively. Combining experimental characterization with theoretical calculation demonstrates the synergistic mechanisms underpinning the enhanced photocatalytic activity. The Pt NCs and In NPs serve as photogenerated electron and hole trapping sites, respectively, which achieves the spatial separation of charge carriers and induces the polarized surface charge distribution, thus fostering optimal adsorption behavior of intermediates. More importantly, the p-block In NPs modulate the electronic microenvironment of Pt NCs to attenuate the adsorption behavior of H* intermediates for accelerated H 2 evolution kinetics. This work unveils a versatile strategy to regulate the electronic structures of dual-metal sites with synergy by establishing charge transfer mechanism for dual-metal cocatalysts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The fabrication of an S-scheme heterojunction demonstrates as an efficient strategy for achieving efficient charge separation and enhancing catalytic activity of piezocatalysts. In this study, a new S-scheme heterojunction was fabricated on the PbBiO 2 Br surface through the photo-deposition of NiO nanoparticles. It was then employed in the piezoelectric catalytic degradation of Rhodamine B (RhB). The results demonstrate that the NiO/PbBiO 2 Br composite exhibits efficient performance in piezocatalytic RhB degradation. The optimal sample is the NiO/PbBiO 2 Br synthesized after 2 h of irradiation, achieving a RhB degradation rate of 3.11 h -1 , which is 12.4 times higher than that of pure PbBiO 2 Br. Simultaneous exposure to visible light and ultrasound further increases in the RhB degradation rate, reaching 4.60 h -1 , highlighting the synergistic effect of light and piezoelectricity in the NiO/PbBiO 2 Br composite. A comprehensive exploration of the charge migration mechanism at the NiO/PbBiO 2 Br heterojunction was undertaken through electrochemical analyses, theoretical calculations, and in-situ X-ray photoelectron spectroscopy analysis. The outcomes reveal that p-type semiconductor NiO and n-type semiconductor PbBiO 2 Br possess matching band structures, establishing an S-scheme heterojunction structure at their interface. Under the combined effects of band bending, interface electric fields, and Coulomb attraction, electrons and holes migrate and accumulate on the conduction band of PbBiO 2 Br and valence band of NiO, respectively, thereby achieving effective spatial separation of charge carriers. The catalyst's synergistic photo-piezoelectric catalysis effect can be ascribed to its role in promoting the generation and separation of charge carriers under both light irradiation and the piezoelectric field. The results of this investigation offer valuable insights into the development and production of catalytic materials that exhibit outstanding performance through the synergy of piezocatalysis and photocatalysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Anisotropic nanostructures with tunable optical properties induced by controllable size and symmetry have attracted much attention in many applications. Herein, we report a controlled synthesis of symmetrically branched AuCu alloyed nanocrystals. By varying Au:Cu atom ratio in precursor, Y-shaped tripods with three-fold symmetry and star-shaped pentapods with five-fold symmetry are synthesized, respectively. The growth mechanism of AuCu tripods from icosahedral seeds and AuCu pentapods from decahedral seeds is revealed. Aiming to excellent photocatalytic performance, CdS nanocrystals are controlled grown onto the sharp tips of AuCu tripods and pentapods. In addition, a carrier-selective blocking layer of Ag 2 S is introduced between AuCu and CdS, for achieving effective charge separation in AuCu-Ag 2 S-CdS nanohybrids. Through evaluating the photocatalytic performance by hydrogen generation experiments, the AuCu-Ag 2 S-CdS tripod nanocrystals exhibit an optimized hydrogen evolution rate of 2182 μmol·g -1 ·h -1 . These findings will contribute greatly to the understanding of complex nanoparticle growth mechanism and provide a strategy for the design of anisotropic nanoalloys for widely photocatalytic applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Lead-free halide perovskites as a new kind of potential candidate for photocatalytic organic synthesis have attracted much attention recently. The rational heterojunction construction is regarded as an efficient strategy to delicately regulate their catalytic performances. Herein, a semi-conductive covalent organic framework (COF) nanosheet, C 4 N, is employed as the functional component to construct Cs 2 AgBiCl 6 /C 4 N (CABC/C 4 N) heterojunction. It is found that the C 4 N nanosheets with rich surface functional groups can serve as heterogeneous nucleation sites to manipulate the growth of CABC nanocrystals and afford close contact between each other, therefore facilitate the transfer and spatial separation of photogenerated charge carriers, as verified by in situ X-ray photoelectronic spectroscopy and Kelvin probe force microscopy. Moreover, the oxygen affinity of C 4 N endows the heterojunctions with outstanding aerobic reactivity, thus improving the photocatalytic performance largely. The optimal CABC/C 4 N heterojunction delivers a thioanisole conversion efficiency of 100% after 6 h, which is 2.2 and 7.7-fold of that of CABC and C 4 N. This work provides a new ideal for the design and application of lead-free perovskite heterojunction photocatalysts for organic reactions., (© 2024 Wiley‐VCH GmbH.)

Bismuth vanadate (BiVO 4 ), as a promising photoanode for photoelectrochemical (PEC) water splitting, suffers from poor charge separation efficiency and light absorption efficiency. Herein, iron oxychloride (FeOCl) is introduced as a novel cocatalyst simply grafted on BiVO 4 to construct an integrated photoanode, enhancing PEC performance. The optimized FeOCl/BiVO 4 photoanode exhibits a superior photocurrent density value of 5.23 mA cm -2 at 1.23 V versus reversible hydrogen electrode (RHE) under AM 1.5G illuminations. From experimental analysis, such high PEC performance is ascribed to the unique properties of FeOCl, facilitating charge transport, increasing light absorption efficiency, and promoting water oxidation kinetics. Density functional theory calculations further confirm that FeOCl optimizes the Gibbs free energy of H and O-containing intermediates (OOH * ) during PEC processes, boosting the catalytic kinetics of PEC water splitting. This work presents FeOCl as a promising catalyst for constructing high efficient PEC water-splitting photoanodes., (© 2024 Wiley‐VCH GmbH.)

Solar cells convert light energy directly into electricity using semiconductor materials. The ternary system, composed of poly(3-hexylthiophene) (P3HT), fullerene (C 60 ), and phenyl-C 61 -butyric-acid-methyl-ester (PCBM), expressed as P3HT-C 60 -PCBM, is one of the most efficient organic solar cells. In the present study, the structures and electronic states of P3HT-C 60 -PCBM have been investigated by means of the density functional theory (DFT) method to shed light on the mechanism of charge separation in semiconductor materials. The thiophene hexamer was used as a model of P3HT. Five geometrical conformers were obtained as the C 60 -PCBM binary complexes. In the ternary system, P3HT wrapped around C 60 in the stable structure of P3HT-C 60 -PCBM. The intermolecular distances for P3HT-(C 60 -PCBM) and (P3HT-C 60 )-PCBM were 3.255 and 2.885 Å, respectively. The binding energies of P3HT + (C 60 -PCBM) and (P3HT-C 60 ) + PCBM were 27.2 and 19.1 kcal/mol, respectively. The charge transfer bands were found at the low-lying excited states of P3HT-C 60 -PCBM. These bands strongly correlated with the carrier separation and electron transfer in solar cells. The electronic states at the ground and excited states of P3HT-C 60 -PCBM were discussed on the basis of the calculated results.