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A general and adaptable method is proposed to reliably extract quantitative information from smartphone images of microfluidic sensors. By analyzing and processing the color information of selected standard substances, the influence of light conditions, device differences, and human factors could be significantly reduced. Machine learning and multivariate fitting methods were proved to be effective for chroma correction, and a key element was the training of sample size and the fitting form, respectively. A custom APP was developed and validated using a high-sensitivity chromium ion quantification paper chip. The average chroma deviations under different conditions were reduced by more than 75% in RGB color space, and the concentration test error was reduced by more than half compared with the commonly used method. The proposed approach could be a beneficial supplement to existing and potential colorimetry-based detection methods. [ABSTRACT FROM AUTHOR]

To enhance the detection performance of hydrogen (H 2), we employed a self-sacrificing template method to prepare a three-dimensional (3D) PdCu-modified Ti 3 C 2 T x nanocomposite, denoted as PdCu/Ti 3 C 2 T x. Within 3D PdCu/Ti 3 C 2 T x nanocomposite, PdCu as the active center component, was evenly distributed on Ti 3 C 2 T x nanosheets. The unique architecture increased the exposure of active center sites, while the Ti 3 C 2 T x nanosheets provided additional gas diffusion channels, thereby contributing to improved gas sensing performance. Comparing to PdCu nanoparticles, PdCu/Ti 3 C 2 T x exhibited an enhancing response and a fast response time of 4 s to 0.5 % H 2. PdCu/Ti 3 C 2 T x also showed an ultra-low detection limit of 0.1 % H 2 and excellent repeatability, selectivity and long-term stability. The outstanding gas sensing performance could be attributed to the 3D structure and the heterostructure between PdCu and Ti 3 C 2 T x. The insights gained from this study provide novel perspectives for designing and synthesizing high-performance gas-sensitive materials. • Three-dimensional PdCu-modified Ti 3 C 2 T x nanocomposites were prepared by self-sacrificing template method. • The PdCu/Ti 3 C 2 T x nanocomposite has excellent sensing characteristics for hydrogen, and the response speed is only 4 s. • The outstanding sensing performance were attributed to the 3D structure and the heterostructure between PdCu and Ti 3 C 2 T x. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ti 4 O 7 synthesized by facile and rapid aluminothermic reduction was applied to improve the Zn–Ni battery. • Ti 4 O 7 simultaneously regulates electrons and Zn(OH) 4 2–, contributing to forming uniform zinc anode. • DFT calculations confirmed that anchoring effect of Ti 4 O 7 on Zn(OH) 4 2– was closely related to the unsaturated bond of Ti 4 O 7. Zn–Ni battery is prospective green energy storage device. However, Zn(OH) 4 2–, the dissolved product of ZnO in the electrolyte, redistributes during the cycle, leading to the shape changing of the anode. This issue severely limits the lifespan of zinc anodes. Despite the success in improving the electrochemical performances of zinc anode via adding Ti 4 O 7 additive, the important mechanism of such modified anode has not been well understood. In addition, the aluminothermic reduction is facile and energy-saving. But the application of Ti 4 O 7 synthesized by this method in Zn–Ni batteries has not been studied. Herein, Ti 4 O 7 synthesized by facile and rapid aluminothermic reduction was applied to alkaline zinc anode. In subsequent electrochemical tests, the discharge capacity and cyclic performance of the zinc-nickel battery was significantly improved by adding as-prepared Ti 4 O 7 particles. At a high discharge current of 2.5 A (34.54 mA cm−2), the anode modified by Ti 4 O 7 delivered higher discharge capacity of 364 mAh g−1, in contrast to the 283 mAh g−1 of pristine anode. Even at ultra-high discharge current of 10 A (138.16 mA cm−2), the battery operated stably for 480 cycles. Besides, the mechanism of Ti 4 O 7 modifying anode was studied in-depth by a variety of characterizations and density functional theory (DFT) calculations. We discovered that Ti 4 O 7 simultaneously regulates the distribution of electrons on the anode and Zn(OH) 4 2– in the electrolyte, contributing to forming uniform zinc anode during cycling. [ABSTRACT FROM AUTHOR]

Conductive TiO x clusters with Ti3+ species and Ti–O 5 unsaturated coordination structure were incorporated into nanosheets-assembled hollow ZnIn 2 S 4 by NH 2 -MIL-125(Ti) as template for solar CO 2 reduction. This typical photocatalysts exhibit highly selective photoreduction of CO 2 , achieving a super high visible-light photocatalytic CO evolution activity. [Display omitted] • Conductive Ti3+-rich TiO x clusters incorporated into hollow semiconductors were synthesized. • The catalyst exhibits high activity and selectivity toward CO 2 photoreduction. • The active sites were identified, inducing efficient trapping of electrons. • This performance is ascribed to efficient charge separation. Solar-driven CO 2 conversion into fuels is a promising solution toward green energy conversion. It is a challenge to regulate the precise structure of photocatalysts at the atomic scale, facilitating the charge transfer and improving CO 2 photoreduction performance. Herein, conductive Ti3+-rich TiO x clusters with unsaturated Ti–O 5 coordination incorporated into nanosheets-assembled hollow sulfide semiconductors were prepared through a versatile transformation strategy by using NH 2 -MIL-125(Ti) metal–organic–framework as precursor. This typical photocatalysts exhibit highly selective photoreduction of CO 2 , achieving a super high visible-light photocatalytic CO evolution activity of 1100 μmol g−1h−1. The active sites were identified on the surface of conductive TiO x clusters, inducing efficient trapping of photogenerated electrons at the interface and suppressing H 2 generation. This enhanced performance is ascribed to Ti3+-rich TiO x clusters as an efficient cocatalyst on sulfide semiconductor providing more active sites due to electrical conductivity and unsaturated coordination environment. This work provides a promising approach to enhance photocatalytic performance of the catalysts coupled by unique metal oxide clusters for selective photoreduction of CO 2. [ABSTRACT FROM AUTHOR]

• Design a high-sensitivity fiber-optic disk accelerometer array based on ultra-weak fiber Bragg gratings. • The novel time-domain difference unwrap algorithm significantly enhances the phase unwrapping capability. • Analyze the influence of noise and higher-order polynomial fitting errors, showing the algorithm order is limited to three. • Improve the dynamic range of the accelerometer by 30 dB compared to the unwrap algorithm. For phase-sensitive fiber-optic accelerometers, the limitation of the unwrap algorithm requires a trade-off between high sensitivity and maximum measurable acceleration. In this work, we have designed a high-sensitivity and a large dynamic range (DR) quasi-distributed fiber-optic disk accelerometer (FODA) array based on ultra-weak fiber Bragg gratings (UWFBG) by employing the time-domain difference unwrap (TDU) algorithm. Theoretical derivations and practical implementations demonstrate that the TDU algorithm can effectively improve the maximum recoverable amplitude (MRA). The FODA array possesses a resonance frequency of 2 kHz, a flat frequency response band from 5 Hz to 630 Hz, excellent linearity with an R2 value of 0.99981, and a sensitivity of 21.46 rad/g at 100 Hz. A DR of 104.82 dB is achieved at 400 Hz with a 10 kHz repetition rate by the 2nd TDU algorithm, which improves 21 dB compared with the unwrap algorithm. [ABSTRACT FROM AUTHOR]

• The role of strong proton adsorption materials in enhancing OER in neutral seawater. • Experiment shows Pd oct -O-Co oct prevents Co restructuring, boosts charge transfer. • Pd single atoms into Co 3 O 4 shifts d-band, boosts metal traits, lowers energy barrier. Direct electrolysis of pH-neutral seawater for hydrogen generation is a promising method for storing renewable energy. However, the oxygen evolution reaction (OER) faces a selectivity challenge, competing with chlorine evolution and confronting severe corrosion issues of the electrode. Here, we have synthesized ultrathin, polycrystalline, porous Co 3 O 4 nanosheets with Pd single atoms (Pd SA -Co 3 O 4) for efficient and stable pH-neutral seawater decomposition. The octahedral Pd-O-Co active unit, generated by the synergistic coordination of the Pd single atom strong proton adsorption (SPA) material with Co 3 O 4 nanosheets, resulted in Pd SA -Co 3 O 4 have activities 3, 5, and 31 times higher than Co 3 O 4 , IrO 2 , and commercial Co 3 O 4 , respectively. It also remained stable in pH-neutral seawater for 80 h. Operando in situ Raman spectroscopy combined with density functional theory calculations showed that synergistic interactions between the strong proton adsorption of Pd single atoms and the active site Co enhanced the adsorption of intermediates and significantly reduced the free energy of adsorption at the rate-determining step (O*→OOH*). The Pd-O-Co active units inhibited the transformation of the dynamic structure of the Co 3 O 4 substrate and reduced the corrosive effect of Cl ions during the OER process. [ABSTRACT FROM AUTHOR]

Nanoreactors with integrated adsorption-catalytic-conversion functionality is employed for the first time to construct iodine host materials. The undesired shuttled/dissolved I 3 − is avoided, which achieves high-performance zinc-iodine batteries. [Display omitted] • The nano-microreactor principle was employed to construct iodine host materials. • Nanoreactors possess integrated adsorption-catalytic-conversion functionality. • Ultrahigh iodine utilization without undesired shuttled/dissolved I 3 − was obtained. Zinc-iodine (Zn-I 2) batteries have attracted considerable interest thanks to their high energy density, low cost, and inherent safety. However, challenges such as dissolution/shuttle of polyiodides and sluggish iodine redox kinetics limit their practical applications. In this paper, a nano-microreactor with highly catalytic center was employed as an iodine host material. Benefiting from the synergistic advantages of the electronic and geometric microenvironments of the nanoreactor, the nanoreactor with integrated adsorption-catalytic-conversion functionality enables the iodine conversion reaction to be carried out in a highly utilizable and stable manner without the undesired intermediate I 3 −, realizing a highly efficient Zn-I 2 conversion reaction. An impressive near-theoretical capacity (213.9 mAh g−1) and ultra-long cycling stability (60,000 cycles at 10 A g−1 accompanied by an initial capacity of up to 164.9 mAh g−1 and capacity retention of 85.4%) were achieved. The nano-microreactor principle with accurate active site location and regulated reaction space will precisely modulate the catalytic program in the nanometer range, which suggests an effective strategy and new inspiration for realizing high-performance Zn-I 2 batteries. [ABSTRACT FROM AUTHOR]

• The CO 2 * tends to dissociate directly to form CO* on the θ-Fe 3 C(031) surface rather than COOH* and HCOO* intermediates. • The CO* tends to desorb forming CO instead of further conversion to hydrocarbons on the θ-Fe 3 C(031) surface. • The high coverage of H* species on the θ-Fe 3 C(031) surface crystals effectively inhibits its further oxidation. • Compared with methane, ethylene and ethane, carbon monoxide shows the highest relative selectivity on the surface of θ-Fe 3 C(031) crystals. Catalytic conversion of carbon dioxide into high-value compounds is a promising strategy for reducing carbon dioxide emissions. In the reduction of CO 2 to hydrocarbons, the active point and reaction mechanism of iron-based catalysts are still unclear. Here, we systematically investigated the complete reaction path of carbon dioxide hydrogenation to methane, ethylene, ethane, and carbon monoxide over the θ-Fe 3 C(031) surface using first principles calculations. The electronic structure analysis shows that carbon dioxide tends to dissociate directly on the θ-Fe 3 C(031) surface to form CO* instead of COOH* and HCOO* intermediates. Due to the high energy barrier for CO* hydrogenation, it tends to desorb forming CO product instead of further transformation into hydrocarbons. In addition, the microkinetic model proved that the H* species coverage on the θ-Fe 3 C(031) crystal surface is highly, which could effectively inhibit the further oxidation of the catalyst, indicating the catalyst to be highly stable. Meanwhile, carbon monoxide behaved the highest relative selectivity. These results reveal the key intermediates and reaction paths of carbon dioxide hydrogenation over θ-Fe 3 C(031) catalyst surface and further illustrate the key factors affecting its product selectivity, providing a theoretical basis and guidance for the design and synthesis of the catalyst. The Carbon dioxide hydrogenation on the surface of θ-Fe3C(031) catalyst exhibits excellent stability and high relative selectivity of CO. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • The pre-adsorption of Cl− on Fe site of dual-atom Fe/Se-NC (Fe/Se-NC-Cl) would enhance the oxygenophilic property of the catalysts. • The Fe/Se-NC-Cl displays high Cl−-corrosion resistance and ORR activity in seawater electrolyte. • Fe/Se-NC-Cl display outstanding ORR on-set and half-wave potentials of 0.88 and 0.75 V, respectively. • Fe/Se-NC-Cl-based seawater battery shows a recorded peak power density of 94 mW cm−2. Seawater batteries (SWBs) are promising energy conversion systems that directly utilize seawater as an electrolyte for converting chemical energy into electricity. The oxygen reduction reaction (ORR) occurs by consuming dissolved oxygen on the cathode electrocatalysts for discharging. However, chloride ions (Cl−) poison the surface catalytic sites of electrocatalysts, and the low dissolved oxygen concentration critically limits the ORR reaction kinetics, reducing the discharging power density and working life. In this work, we designed and synthesized the Fe/Se-NC electrocatalyst using a facile solution chemical process. Theoretical calculation and experimental results suggest that the incorporation of Se in Fe/Se-NC can significantly enhance the adsorption energy of Cl− on one side of the Fe site (designated as Fe/Se-NC-Cl) and result in the enhanced oxygenophilic property of Fe/Se-NC on another side of the Fe site. This simultaneously enhances Cl-corrosion resistance and ORR activity. The Fe/Se-NC-Cl electrocatalysts display outstanding ORR onset and half-wave potentials of 0.88 and 0.75 V, respectively, which rank at the top among ORR electrocatalysts in natural seawater electrolyte. The SWBs using Fe/Se-NC-Cl as cathodes show a high peak power density of 94 mW cm−2, stability of more than 450 h, and discharge capacity of 583 Wh kg−1 at a current density of 5 mA cm−2 in natural seawater electrolyte. The developed SWB package can efficiently power household appliances with a rated power of up to 50 W. [ABSTRACT FROM AUTHOR]

• The C 2 H 2 molecules are adsorbed in the pore channel of PCN-200 in a commensurate manner. • Dynamic separation of C 2 H 2 /CO 2 is achieved. • The C 2 H 2 molecule is strongly oriented to the two uncoordinated oxygen atoms on the pore surface with a side-on style. Separating acetylene and carbon dioxide is a significant challenge due to their similar physicochemical properties. Herein, we reported an ultramicroporous metal–organic framework, PCN-200, which possesses narrow zig-zag one-dimensional channels with a size of about 4.5 Å. The pore surface of PCN-200 features numerous uncoordinated oxygen polar sites that are symmetrically distributed, facilitating the strong and commensurate binding of acetylene molecules (57.0 kJ mol−1). At 298 K and 1 bar, PCN-200 demonstrates a high selectivity (6.4) towards acetylene over carbon dioxide, and this separation performance is validated through dynamic breakthrough experiments. Simulation studies were conducted to gain insight into the adsorption mechanism for acetylene and carbon dioxide molecules in PCN-200. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The selective promotion of CH 3 OH in CO 2 hydrogenation correlates to Pd-Cu alloy content. • Pd-Cu combination shifts adsorption towards weakly-bonded H 2 and CO 2. • Weakly-bonded H 2 and CO 2 species over Pd-Cu appear to correlate with CH 3 OH promotion. • DFT study rationalizes CO 2 adsorption and initial hydrogenation on Pd-Cu bimetallic surface. Abstract A strong synergetic effect was observed in our previous work on Pd-Cu bimetallic catalysts for CH 3 OH formation from CO 2 hydrogenation when the Pd/(Pd + Cu) atomic ratio lied within 0.25–0.34. In the present study, the importance of Pd-Cu alloy in selective CH 3 OH promotion was evidenced and correlated with alloy contents quantitatively through X-ray diffraction (XRD), scanning transmission electron spectroscopy with energy-dispersive X-ray spectroscopy (STEM/EDS), and H 2 -O 2 titration and N 2 O titration. The surface chemical properties of Pd-Cu combinations were characterized by H 2 -/CO 2 -temperature-programmed desorption (TPD), diffuse reflectance infrared FT spectroscopy (DRIFTS), and density functional theory (DFT), and experimentally evaluated along with monometallic counterparts. Detailed characterization results reveal a unique shift in adsorption towards weakly-bonded H 2 and CO 2 on Pd-Cu bimetallic surface which appear to correlate to the CH 3 OH promotion. DFT calculations on adsorption properties of H 2 and CO 2 show good agreement with the observation from TPD experiments. DFT study also provides insights into the impact of Pd-Cu combination on the activation and initial hydrogenation of CO 2 to formate (HCOO∗) and hydrocarboxyl (COOH∗) intermediates. HCOO∗ formation was found to be kinetically more favored than COOH∗ on monometallic Cu and Pd-Cu surfaces. The lowest barrier for HCOO∗ formation was observed at Pd/(Pd + Cu) atomic ratio of 0.33, around which a good CO 2 conversion and high methanol selectivity were achieved experimentally. [ABSTRACT FROM AUTHOR]

Mixed hierarchical lanthanide metal-organic framework (Ln-MOF) with core-shell structure has been acquired via a solution-mediated epitaxial growth method, retaining the spatially segregated structure of network and domain fluorescence property. The excellent heterostructured characteristics of Ln-MOFs enable the effective electron modulation, multiple energy transfer and thereby remarkably increase recognizing and sensing capacity in phosphate (Ps) or adenosine triphosphate (ATP). Ln3+ centers coupled with Ps or ATP could trigger a decrease in fluorescence of Ln3+, and further interrupt original fluorescence intensity ratio of Tb3+/Eu3+ (I 545 /I 616) to shape the ratiometric fluorescent register. The optimized Tb/Eu-MOF with Tb/Eu ratio of 1:1 presented good linearity responsive to Ps and ATP with lower detection limit of 84.1 nM and 121.4 nM, respectively. Meanwhile, the interference and toxicity experiments have confirmed its high selectivity and high biocompatibility. Thus, the probe could be applied to detect Ps in real environmental water and biologically imaging ATP in Hela cells. This has provided a new strategy to construct Ln-system heterojunction with multiplexed luminescence selectivity and sensitivity in substance detection. • The Tb/Eu-MOF ratiometric fluorescence sensor efficiently detects PO43- and ATP system with lower LOD. • It could be used to detect PO43- in real environmental water and biologically imaging ATP in Hela cells. • DFT and in-situ XPS confirmed the energy transfer model and detection mechanism. [ABSTRACT FROM AUTHOR]

The dual Z-scheme MCZ-7.5 heterojunction coupled with photocatalysis and photo-induced Fenton reaction could degrade 99.7% of MB and 97% of OTC in water within 30 s and 5 min, respectively, much better than that of photocatalysis and Fenton degradation alone. [Display omitted] • The dual Z-scheme heterojunction regulated electron transfer and charge separation efficiency. • MCZ-7.5 promoted the Fe2+/Fe3+ switch by coupling high valent Mo5+ and the fleeding electron. • MCZ-7.5 accelerated Fenton activation in dye and antibiotic degradation. • The dual Z-scheme mechanism and the degradation pathway were further evidenced by DFT. The synergistic effects of photocatalytic activation Fenton reaction is considered to be a promising method to degrade the organic contaminant. Herein, a dual Z-scheme MoS 2 @g-C 3 N 4 /ZIF-8(Zn) (donated as MCZ) heterojunction is designed via a simple assembly approach. The ultraviolet photoelectron spectroscopy (UPS), Mott-Schottky curves (M-S), transient photovoltage (TPV), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculation reveal the electron transfer from n-type g-C 3 N 4 or ZIF-8(Zn) to p-type MoS 2 , providing the platform for band construction and dual Z-scheme model. The optional modulation of the MCZ-x conjunction has efficiently separated photogenerated charge and significantly reactive species through Fenton activation under visible light irradiation. The results indicate that the degradation efficiency of methylene blue (MB) and oxytetracycline (OTC) by MCZ-7.5 could reach 99.7% and 97% only within 30 s and 5 min, respectively, much higher than that of MCZ + vis and MCZ + Fenton. Electron-spin-resonance (ESR) and radical scavenger experiments confirm that the ·OH and ·O 2 – are the dominated reactive oxygen species (ROS). It is speculated the MoS 2 based double Z-pathway heterostructure can accelerate coupling effect of photocatalytic and Fenton reaction in solving practical environmental issues. [ABSTRACT FROM AUTHOR]

To date, the efficient photocatalytic conversion of CO 2 into high-value C2 products remains a great challenge. Herein, the Au-CeO 2 nanocomposite with Au-O-Ce sites at the micro-interface was developed to achieve a highly selective conversion of CO 2 into C 2 H 6. This can be partially ascribed to the formation of key intermediates of COCO* was confirmed via in-situ Fourier transform infrared (FTIR) spectroscopy, indicating that the Au-CeO 2 micro-interface could prompt the multi-electron reduction of CO* before desorption, and enable the production of C2 species. Moreover, theoretical calculations suggested that Au-O-Ce sites at the micro-interface could reduce the energy barriers for the formation of COOH* and COCO*, facilitating the production of C 2 H 6. Therefore, the Au-CeO 2 nanocomposite exhibited a C 2 H 6 production rate of 11.07 µmol g−1 h−1 and high electron selectivity of 93.1 % (product selectivity: 65.3 %), which is comparable with most state-of-the-art photocatalysts. [Display omitted] • Au-CeO 2 nano-photocatalyst realizes highly selective photocatalytic reduction of CO 2 to ethane. • The electron selectivity of ethane is 93.1 % (product selectivity: 65.3 %). • The working mechanism is verified by theoretical calculation and in-situ spectroscopy. • Au-O-Ce active sites are formed on the Au-CeO 2 micro-interface. • The Au-O-Ce site is shown to be critical for the formation of C2 products. [ABSTRACT FROM AUTHOR]

Photocatalytic oxidation is an attractive approach for biomass valorization, but uncontrollable reactive oxygen species (ROS) inevitably initiates over-oxidation of target product, leading to low selectivity. Here we report that combining MnO 2 , WO 3 with carbon nitride (CN) enables the construction of photocatalyst with electron transport channels and oxygen adsorption sites. Owing to the rapid transfer of photo-generated electrons to adsorbed O 2 , CN-WO 3 @MnO 2 exhibited 13.5 and 1.18 times higher 1O 2 and ∙O 2 - generation capacity than CN-WO 3 with 92.8% lower ∙OH generation capacity, respectively. With the synergistic effect of ∙O 2 - and 1O 2 , 2,5-diformylfuran (DFF) selectivity up to 79.6% at high 5-hydroxymethylfurfural (HMF) conversion (77.6%) was attained. Both experimental results and density functional theory calculations indicate that the construction of electron transport channels and oxygen adsorption sites can deliberately modulate the generation of ROS with desired oxidation ability, thus facilitating the efficient and selective oxidation of HMF into DFF. [Display omitted] • The oxidation of HMF to DFF is achieved by the synergistic effect of ∙O 2 - and 1O 2. • Efficient electron transport channels and oxygen adsorption sites was constructed. • The catalyst exhibited DFF yield of 61.8% with selectivity up to 79.6%. [ABSTRACT FROM AUTHOR]

[Display omitted] • The inter-relation between UiO-66 defects and Sb(V) removal performance was revealed. • Different modulators induced UiO-66-Xs with various defect concentrations. • The performance of UiO-66-TFA with the most defects was 2.98 times of that of UiO-66. • The enhanced Sb(V) adsorption was demonstrated by experiments and DFT calculations. Metal-organic frameworks (MOFs) with ability to create rich defects in the structures for exposed binding sites are beneficial for wastewater treatment. However, the inter-relation between the defect concentration and heavy metal removal performance still deserves the exploration. Herein, UiO-66-X crystal materials are successfully synthesized in the presence of monocarboxylic acid of acetic, benzoic, and trifluoroacetic acid, and the effect of defect concentration on Sb(V) removal performance is systematically studied. XRD, TG, EPR and XPS characterizations reveal that the addition of modulators increases the content of defects in the UiO-66-X, which is beneficial to improve the sites utilization. As expected, the Sb(V) adsorption properties of UiO-66-AA, UiO-66-BA and UiO-66-TFA are boosted by 54.1%, 140.0% and 197.7% compared to that of pristine UiO-66. Density functional theory (DFT) calculations further confirm that UiO-66-TFA with the most defects exhibits lower adsorption energy and higher charge transfer, significantly improving the uptake performance of Sb(V). Additionally, the UiO-66-TFA successfully removes antimony in actual water from the Tianyi Lake and Ganjiang River with residual concentrations below 5 μg L−1, meeting the drinking water standard. This work provides guidance for the rational selection of modulators for efficient heavy metal removal from wastewater. [ABSTRACT FROM AUTHOR]

Specific πδ+–πδ- interaction between –C≡C– with vertical π bond in conjugated microporous polymers and electron-rich Pd center with π 5 8 δ - in PdCl 4 2- is constructed, resulting in highly selective capture of PdCl 4 2- in coexistence systems of heavy metals. It provides a novel design principle for efficient and targeted heavy metal adsorbents in acid wastewater. [Display omitted] • Three kinds of CMPs adsorbents were prepared by S-H coupling reactions. • The –C≡C– groups of CMPs were identifified as the adsorption sites of PdCl 4 2-. • Strong πδ+–πδ- interaction was formed between the –C≡C– and PdCl 4 2-. • CMPs exhibited an excellent PdCl 4 2- selectivity in acid water. The targeted capture of heavy metals from wastewater is urgently necessary in response to strategic demands of sustainable resource utilization, but it is severely hampered by the formation of specific adsorbent-adsorbate interactions. Herein, the conjugated microporous polymer CMP-1 with –C≡C– binding sites is introduced for the adsorption of PdCl 4 2- in acid wastewater. The matched interaction between –C≡C– with vertical π bond and electron-rich Pd center with π 5 8 δ - exhibits exceptional PdCl 4 2- selectivity in competitive systems with coexisting heavy metals. To regulate the electron density of π bond in –C≡C– to further reinforce the πδ+–πδ- interaction, p -FCMP and o -FCMP adsorbents are rationally designed through the substitution of electro-withdrawing F group at different positions. A joint experimental-simulation exploration reveals that the F-induced electron oriented migration in –C≡C– results in the decreased π-electron density, therefore enhancing the binding of PdCl 4 2-. Notably, o -FCMP possesses the maximum positive charge density at –C≡C– binding sites, which greatly promotes the charge transfer between –C≡C– and PdCl 4 2- for stronger bonding interaction, achieving an optimal adsorption capacity of 447.7 mg g−1 as well as enhanced selectivity. This work provides unique insights into the efficiently targeted removal of heavy metals. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ligand-engineering strategy was implemented to remove Sb(V). • La- meta -PTAs received better performance owing to more interior active sites. • La-MGs obtained the record high Sb(V) removal performance of 896.5 mg/g. • The enhanced Sb(V) performance was derived from lower adsorption energy. MOFs-based adsorbents with electronic complexity and steric diversity become promising platform for heavy metal wastewater treatment. However, experimentally confirming the effect of ligand effects on Sb(V) adsorption with MOFs materials has remained a fundamental challenge. Herein, ligand-engineering strategy are implemented to synthesize five absorbents (La- para -PTAs, La- ortho -PTAs, La- meta -PTAs, La-MCs and La-MGs) and propose that the adsorption performance is correlate directly with of the utilization of accessible adsorption site. Within the meta -substituted –COOH coordination and imidazole ring, La-MGs achieve almost 92% site utilization promoting the state-of-the-art value of 896.5 mg/g for Sb(V) removal. Rational change of –COOH substituent locations from La- para -PTAs to La- meta -PTAs results in larger BET surface area and bigger pore volume, improving the accessibility of adsorption sites. Based on XPS results and DFT calculations, the strong interaction between La-MGs and Sb(V), which significantly promotes the charge transfer of removal process and increases the content of electron state around the Fermi energy in La 5d and 6 s orbits thus lower the adsorption energy of La-MGs for Sb(V). This work provides insights into the rational design of the definitive structure of MOFs-based adsorbents with tunable adsorption performance for efficient energy conversion toxic metal oxyanion remediation from the viewpoint of adsorption sites utilization. [ABSTRACT FROM AUTHOR]

Construction of heterostructures can circumvent the shortcomings of 2D material components and has potential for applications in optoelectronic devices. Therefore, further development and construction of novel 2D materials is highly important. In this paper, a seamless lateral heterostructure (LHS) based on arsenene (As) and antimonene (Sb) along armchair (AC) and zigzag (ZZ) interfaces is predicted, and the band structures and optical absorption properties with the different interfaces are calculated from first principles. An indirect to direct band structure transition can be observed when the LHS interface changes from AC to ZZ. Additionally, the band gaps of the different (AC and ZZ) heterostructure types exhibit strong atomic number dependences, and can be narrowed from 1.1 to 0.45 eV and from 0.57 to 0.50 eV, respectively. The partial density of states (PDOS) and the conduction band minimum-valence band maximum (CBM-VBM) characteristics clarify the contributions from the different orbits to the band structures around the Fermi level. It should be noted that As/Sb lateral heterostructures have unique optical absorption characteristics in the mid-infrared range. Our predictions highlight the potential applications of As and Sb LHSs in electronics and optoelectronics. These results provide another 2D material with potential applications in mid-infrared optoelectronic devices. • Predict a lateral heterostructure made from As and Sb with armchair and zigzag interfaces. • Indirect to direct band structure change occurs with armchair to zigzag variation. • The lateral heterostructure band gaps narrowed to 0.50 eV for zigzag. • Unique optical absorption characteristics are found in the mid-infrared range. [ABSTRACT FROM AUTHOR]

[Display omitted] • The dual reaction centers ZnO@FePc photo-Fenton catalyst was constructed through surface hydroxyl-induced assembly. • Ibuprofen degraded more than 90 % within 10 min under simulated sunlight over ZnO@FePc catalyst. • The disproportionation and oxidation of hydroxyl groups promote the formation of electron transfer channel. • The electron transfer between ZnO and FePc is crucial for the excellent degradation performance. To achieve efficient degradation of pharmaceutical and personal care products (PPCPs), dual reaction centers ZnO@FePc photo-Fenton catalysts with high-speed electron transmission channel were designed through surface hydroxyl-induced assembly. In ZnO@FePc catalytic system, the photocatalysis center of ZnO and Fenton catalytic center of FePc were formed simultaneously. Concept and process for the control of hydroxyl groups to construct a dual reaction center ZnO@FePc photo-Fenton catalyst were verified ingeniously based on the density functional theory (DFT) analysis and experimental results. A series of catalysts, including ZIF-8 (400 ℃-N 2), FePc (400 ℃-N 2), ZIF-8 (400 ℃)-FePc (400 ℃) and ZnO@FePc were prepared and characterized by XRD, FTIR, TEM, BET, XPS, PL and DRS, respectively. The ZnO@FePc catalyst showed superior performance for the photo-Fenton degradation of ibuprofen, affording degradation rate larger than 90 % within just 10 min under simulateed sunlight. The excellent performance of ZnO@FePc catalyst is mainly attributed to the synergistic effect between dual reaction centers of ZnO@FePc. This work provides a novel method to construct dual reaction centers ZnO@FePc catalyst with efficient photo-generated electrons transmission link and to strengthen the synergistic effect of dual reaction centers. [ABSTRACT FROM AUTHOR]

The utilization of a heterogeneous nanojunction design has shown significant enhancements in the gas sensing capabilities of traditional metal oxide gas sensors. In this study, a novel room temperature H 2 S gas sensor employing Fe 2 O 3 functionalized Ti 3 C 2 MXene as the sensing material has been developed. This sensor exhibits a broad detection range (0.01-500 ppm), low detection limit (10 ppb), and rapid response/recovery times (10 s/15 s), making it ideal for ppb-level H 2 S detection. The exceptional gas sensitivity of Fe 2 O 3 /Ti 3 C 2 composite to H 2 S can be attributed to several key factors. First, the unique layered frame structure of Fe 2 O 3 /Ti 3 C 2 significantly amplifies the surface area of the hybrid material, enhancing the absorption and diffusion capabilities of H 2 S molecules. Second, the abundance of functional groups (-O, -OH, and -F) on the surface of Ti 3 C 2 MXene nanosheets provides additional active sites for H 2 S adsorption, The density functional theory calculation confirms that the adsorption energy of the Fe 2 O 3 /Ti 3 C 2 composite for H 2 S (-2.93 eV) is significantly lower than that of pure Fe 2 O 3 (-2.37 eV) and Ti 3 C 2 (-0.2 eV). Lastly, the remarkable metal conductivity of Ti 3 C 2 MXene ensures efficient electron transfer, thereby enhancing overall sensing performance.

The seawater battery (SWB) holds great potential as the next-generation energy supply system for marine electrical equipment. However, its efficiency and durability are hindered by low oxygen concentration and harmful Cl - adsorption and corrosion in seawater. Herein, a host-guest strategy is developed to fabricate diatomic catalysts with adjacent Co and Ni sites on nitrogen-doped carbon (CoNi-DAC), where Co and Ni atoms are each coordinated to three nitrogen atoms. Theoretical calculations and in situ characterization reveal that the synchronized reduction of Co and Ni valence states enhances ORR kinetics by optimizing the O 2 adsorption energy barrier, facilitating direct O─O bond cleavage and preventing *OOH intermediate formation. This electronic modulation enhances oxygenophilicity and Cl - corrosion resistance. The Co/Ni diatomic sites synergistically improve ORR catalytic activity, achieving a half-wave potential (E 1/2 ) of 0.79 V and exceptional long-term durability of nearly 700 h in natural seawater. The assembled SWB with CoNi-DAC coated carbon brush electrode attains a peak power density of 3.3 W L -1 . This work offers valuable insights into the design and development of advanced ORR electrocatalysts for natural seawater environments., (© 2024 Wiley‐VCH GmbH.)

The development of a highly efficient, stable, and low-cost bifunctional catalyst is imperative for facilitating the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, significant challenges are involved in extending its applications to rechargeable zinc-air batteries. This study presents a bifunctional catalyst, Zr 2 ON 2 @NiFe layered double hydroxide (LDH), that was developed by utilizing a urea-glass route for synthesizing the Zr 2 ON 2 precursor, followed by riveting NiFe LDH nanosheets using a hydrothermal method. Specifically, the vertical distribution of NiFe LDH on the Zr 2 ON 2 surface ensures the maximization of the number of accessible active sites and interfacial catalysis of NiFe LDH. Notably, Zr 2 ON 2 @NiFe LDH demonstrates ORR and OER bifunctional electrocatalytic behavior and high stability owing to its heterostructure and composition. Furthermore, a rechargeable zinc-air battery using a Zr 2 ON 2 @NiFe LDH electrocatalyst as the air cathode demonstrated a high peak power density (172 mW cm -2 ) and galvanostatic charge-discharge cycle stability (5 mA cm -2 over 443 h). Thus, this study presents an efficient and cost-effective strategy for the design of bifunctional electrocatalysts., 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.)

Atomically dispersed single atom (SA) and atomic cluster (AC) metallic materials attract tremendous attentions in various fields. Expanding monometallic SA and AC to multimetallic SA/AC composites opens vast scientific and technological potentials yet exponentially increasing the synthesis difficulty. Here, we present a general energy-selective-clustering methodology to build the largest reported library of carbon supported bi-/multi-metallic SA/AC materials. The discrepancy in cohesive energy results into selective metal clustering thereby driving the symbiosis of multimetallic SA or/and AC. The library includes 23 bimetallic SA/AC composites, and expanded compositional space of 17 trimetallic, quinary-metallic, septenary-metallic SA/AC composites. We chose bimetallic M 1 SA M 2 AC to demonstrate the electrocatalysis utility. Unique decoupled active sites and inter-site synergy lead to 8/47 mV overpotential at 10 mA cm -2 for alkaline/acidic hydrogen evolution and over 1000 h durability in water electrolyzer. Moreover, delicate modulations towards composition and configuration yield high-performance catalysts for multiple electrocatalysis systems. Our work broadens the family of atomically dispersed materials from monometallic to multimetallic and provides a platform to explore the complex composition induced unconventional effects., (© 2024. The Author(s).)

Strain engineering is an effective strategy to improve the activity of catalysts, especially for flexible carbon-based materials. Nitrogen-coordinated single atomic metals on a carbon skeleton (M-N x /C) are of interest in catalytic electroreduction reactions due to their high activity and atomic utilization. However, the effect of strain on the structure-activity relationship between the electrochemical activity and the electronic and geometric structures of Ni-N x /C remains unclear. Here, we found that by applying tensile strain on the Ni-N 4 /C, the spin state of the single atom can be changed from a low-spin to a high-spin state. Moreover, the energy gap between the highest occupied d orbital of Ni and the lowest unoccupied molecular orbital of the adsorbed species narrowed. With an increasing strain rate, the catalytic activity of O 2 and CO 2 electroreduction can be improved. Especially for the 2e - O 2 reduction, the implicit solvent model, constant-potential method, and microkinetic model were used to verify the positive effect of suitable stretching on the catalytic activity from thermodynamic and kinetic viewpoints. This work can reveal the relationship between strain, spin state, and the catalytic activity of Ni-N x /C.

Atomically dispersed Fe-N-C catalysts emerged as promising alternatives to commercial Pt/C for the oxygen reduction reaction. However, the majority of Fe-N-C catalysts showed unsatisfactory activity and durability due to their inferior O-O bond-breaking capability and rapid Fe demetallization. Herein, we create a pseudo-phthalocyanine environment coordinated diatomic iron (Fe 2 -pPc) catalyst by grafting the core domain of iron phthalocyanine (Fe-N α -C α -N β ) onto defective carbon. In situ characterizations and theoretical calculation confirm that Fe 2 -pPc follows the fast-kinetic dissociative pathway, whereby Fe 2 -pPc triggers bridge-mode oxygen adsorption and catalyzes direct O-O radical cleavage. Compared to traditional Fe-N-C and FePc-based catalysts exhibiting superoxo-like oxygen adsorption and an *OOH-involved pathway, Fe 2 -pPc delivers a superior half-wave potential of 0.92 V. Furthermore, the ultrastrong N α -C α bonds in the pPc environment endow the diatomic iron active center with high tolerance for reaction-induced geometric stress, leading to significantly promoted resistance to demetallization. Upon an unprecedented harsh accelerated degradation test of 150,000 cycles, Fe 2 -pPc experiences negligible Fe loss and an extremely small activity decay of 17 mV, being the most robust candidate among previously reported Fe-N-C catalysts. Zinc-air batteries employing Fe 2 -pPc exhibit a power density of 255 mW cm -2 and excellent operation stability beyond 440 h. This work brings new insights into the design of atomically precise metallic catalysts.

The creation of frustrated Lewis pairs on catalyst surface is an effective strategy for tuning CO 2 activation. The critical step in the formation of frustrated Lewis pairs is the spatial effect of proximal Lewis acid-Lewis base pairs. Here, we demonstrate a facile surface functionalization methodology that enables hydrogen bonding between N and H atoms to mediate the construction of frustrated Lewis pairs in poly(heptazine imide), thereby increasing the propensity to activate CO 2 molecules. Experimental and theoretical results show that the construction of active hydrogen bonding regions can facilitate the bending of CO 2 molecules. Furthermore, the delocalization of electron clouds induced by the hydrogen bonding-mediated frustrated Lewis pairs can promote the heterolytic cleavage and photocatalytic conversion of CO 2 . This work highlights the potential of utilizing hydrogen bonding-mediated strategy in heterogeneously photocatalytic activation of CO 2 over polymer materials., (© 2024 Wiley-VCH GmbH.)

Cu-based catalysts have been shown to selectively catalyze CO 2 photoreduction to C 2+ solar fuels. However, they still suffer from poor activity and low selectivity. Herein, we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N 2 motif (Cu-N 2 -V). Lead many recently reported photocatalysts and its Cu-N 3 and Cu-N 4 counterparts, Cu-N 2 -V exhibits superior photocatalytic activity for CO 2 reduction to ethanol and delivers 69.8 μmol g -1  h -1 ethanol production rate, 97.8 % electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N 3 and Cu-N 4 . Revealed by the extensive experimental investigation combined with DFT calculations, the superior photoactivity of Cu-N 2 -V stems from its defected Cu-N 2 configuration, in which the Cu sites are electron enriched and enhance electron delocalization. Importantly, Cu in Cu-N 2 -V exist in both Cu + and Cu 2+ valence states, although predominantly as Cu + . The Cu + sites support the CO 2 activation, while the co-existence of Cu + /Cu 2+ sites are highly conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C-C coupling. Furthermore, the hollow microstructure of the catalyst also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N 2 -V an effective and high-performance catalyst for the solar-driven CO 2 conversion to ethanol. This study also elucidates the C-C coupling reaction path via *CO-*CO to *COCOH and rate-determining step, and reveals the valence state change of partial Cu species from Cu + to Cu 2+ in Cu-N 2 -V during CO 2 photoreduction reaction., (© 2024 Wiley-VCH GmbH.)

Single-molecule localization methods have been popularly exploited to obtain super-resolved images of biological structures. However, the low blinking frequency of randomly switching emission states of individual fluorophores greatly limits the imaging speed of single-molecule localization microscopy (SMLM). Here we present an ultrafast SMLM technique exploiting spontaneous fluorescence blinking of cyanine dye aggregates confined to DNA framework nanostructures. The DNA template guides the formation of static excimer aggregates as a "light-harvesting nanoantenna", whereas intermolecular excitation energy transfer (EET) between static excimers causes collective ultrafast fluorescence blinking of fluorophore aggregates. This DNA framework-based strategy enables the imaging of DNA nanostructures with 12.5-fold improvement in speed compared to conventional SMLM. Further, we demonstrate the use of this strategy to track the movement of super-resolved DNA nanostructures for over 20 min in a microfluidic system. Thus, this ultrafast SMLM holds great potential for revealing the dynamic processes of biomacromolecules in living cells.

Metal-organic frameworks have garnered attention as highly efficient pre-electrocatalysts for the oxygen evolution reaction (OER). Current structure-activity relationships primarily rely on the assumption that the complete dissolution of organic ligands occurs during electrocatalysis. Herein, modeling based on NiFe Prussian blue analogs (NiFe-PBAs) show that cyanide ligands leach from the matrix and subsequently oxidize to corresponding inorganic ions (ammonium and carbonate) that re-adsorb onto the surface of NiFe OOH during the OER process. Interestingly, the surface-adsorbed inorganic ions induce the OER reaction of NiFe OOH to switch from the adsorbate evolution to the lattice-oxygen-mediated mechanism, thus contributing to the high activity. In addition, this reconstructed inorganic ion layer acting as a versatile protective layer can prevent the dissolution of metal sites to maintain contact between catalytic sites and reactive ions, thus breaking the activity-stability trade-off. Consequently, our constructed NiFe-PBAs exhibit excellent durability for 1250 h with an ultralow overpotential of 253 mV at 100 mA cm -2 . The scale-up NiFe-PBAs operated with a low energy consumption of ∼4.18 kWh m -3 H 2 in industrial water electrolysis equipment. The economic analysis of the entire life cycle demonstrates that this green hydrogen production is priced at US$2.59/ [Formula: see text] , meeting global targets (

As a novel electrochemical energy conversion device, direct ethanol fuel cells are currently encountering two significant challenges: CO poisoning and the difficulty of C-C bond cleavage in ethanol. In this work, an amorphous PdS nanowires/ultrafine IrMnO x bimetallic oxides (denoted as a-PdS/IrMnO x NWs) catalyst with abundant oxide/metal (crystalline/amorphous) inverse heterogeneous interfaces was synthesized via a hydrothermal process succeeded by a nonthermal air-plasma treatment. This unique interfacial electronic structure along with the incorporation of oxyphilic metal has resulted in a significant enhancement in the electrocatalytic performance of a-PdS/IrMnO x NWs toward the ethanol oxidation reaction, achieving current densities of 12.45 mA·cm -2 and 3.68 A·mg Pd -1 . Moreover, the C1 pathway selectivity for ethanol oxidation has been elevated to 47%, exceeding that of other as-prepared Pd-based counterparts and commercial Pd/C catalysts. Density functional theory calculations have validated the findings that the decoration of IrMn species onto the amorphous PdS surface has induced a charge redistribution in the interface region. The redistribution of surface charges on the a-PdS/IrMnO x NWs catalyst results in a significant decrease in the activation energy required for C-C bond cleavage and a notable weakening of the CO binding strength at the Pd active sites. Consequently, it enhanced both the EOR C1 pathway selectivity and CO poisoning resistance to the a-PdS/IrMnO x NWs catalyst.

Developing highly active oxygen evolution reaction (OER) catalysts in acidic conditions is a pressing demand for proton-exchange membrane water electrolysis. Manipulating proton character at the electrified interface, as the crux of all proton-coupled electrochemical reactions, is highly desirable but elusive. Herein we present a promising protocol, which reconstructs a connected hydrogen-bond network between the catalyst-electrolyte interface by coupling hydrophilic units to boost acidic OER activity. Modelling on N-doped-carbon-layer clothed Mn-doped-Co 3 O 4 (Mn-Co 3 O 4 @CN), we unravel that the hydrogen-bond interaction between CN units and H 2 O molecule not only drags the free water to enrich the surface of Mn-Co 3 O 4 but also serves as a channel to promote the dehydrogenation process. Meanwhile, the modulated local charge of the Co sites from CN units/Mn dopant lowers the OER barrier. Therefore, Mn-Co 3 O 4 @CN surpasses RuO 2 at high current density (100 mA cm -2 @ ~538 mV)., (© 2024 Wiley‐VCH GmbH.)

High-fidelity patterning of DNA origami nanostructures on various interfaces holds great potential for nanoelectronics and nanophotonics. However, distortion of a DNA origami often occurs due to the strong interface interactions, e.g., on two-dimensional (2D) materials. In this study, we discovered that the adsorption of silica precursors in rapid silicification can prevent the distortion caused by graphene and generates a high shape-fidelity DNA origami-silica composite on a graphene interface. We found that an incubation time of 1 min and silicification time of 16 h resulted in the formation of DNA origami-silica composites with the highest shape fidelity of 99%. By comparing the distortion of the DNA origami on the graphene interface with and without silicification, we observed that rapid silicification effectively preserved the integrity of the DNA origami. Statistical analysis of scanning electron microscopy data indicates that compared to bare DNA origami, the DNA origami-silica composite has an increased shape fidelity by more than two folds. Furthermore, molecular dynamics simulations revealed that rapid silicification effectively suppresses the distortion of the DNA origami through the interhelical insertion of silica precursors. Our strategy provides a simple yet effective solution to maintain the shape-fidelity DNA origami on interfaces that have strong interaction with DNA molecules, expanding the applicable interfaces for patterning 2D DNA origamis.

A ratiometric fluorometry based on silicon quantum dots (SiQDs) and gold nanoclusters (AuNCs) is constructed for detecting activity of butyrylcholinesterase (BChE) in human serum. By using thiobutyrylcholine iodide (BTCh) as the substrate of BChE-catalyzed hydrolysis reaction, variation of fluorescence emission from AuNCs is employed as an indicator of BChE activity since one of the hydrolysis products, thiocholine (TCh), would influence the aggregation state of AuNCs and consequently led to the change of fluorescence quantum efficiency of AuNCs. It is interesting that there are two mechanisms working for the fluorescence emission of aggregated AuNCs: aggregation-induced emission enhancement (AIEE) and aggregation-caused quenching (ACQ) with the presence of TCh at very low and higher concentration levels, respectively. Although both of these mechanisms can be utilized for sensing BChE, their opposite influence on the fluorescence emission of aggregated AuNCs should be worthy of attention, especially in the process of developing fluorescence methods for detecting trace targets by using AuNCs. In order to eliminate the fluctuation of fluorophotometer, SiQDs is chosen as the fluorophore to develop by ratiometric fluorescence methods in this work. Additionally, obvious aggregation of AuNCs induces significant decrease of inner filter effect (IFE) on the fluorescence emitted from SiQDs, while mild aggregation of AuNCs demonstrates little IFE. The linear ranges for detecting activity of BChE are 0.004 - 0.05 U/L and 0.5 - 20 U/L by ratiometric fluorometry based on the AIEE and ACQ, respectively. The very different responses originated from AIEE and ACQ of AuNCs would respectively make their own contributions to the determination of BChE activities at very low or high levels, which facilitate the developments of enhanced or quenched fluorescence methods. However, the detection of BChE activities at medium levels might suffer from the combination of AIEE and ACQ with ambiguous fractions. Therefore, it must be careful during the processes of developing and applying fluorescence methods based on the AIEE and ACQ of AuNCs, as well as the process of evaluating their analytical performance., 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.)

DNA monolayers with inherent chirality play a pivotal role across various domains including biosensors, DNA chips, and bioelectronics. Nonetheless, conventional DNA chiral monolayers, typically constructed from single-stranded DNA (ssDNA) or double-stranded DNA (dsDNA), often lack structural orderliness and design flexibility at the interface. Structural DNA nanotechnology has emerged as a promising solution to tackle these challenges. In this study, we present a strategy for crafting highly adaptable twisted DNA origami-based chiral monolayers. These structures exhibit distinct interfacial assembly characteristics and effectively mitigate the structural disorder of dsDNA monolayers, which is constrained by a limited persistence length of ∼50 nm of dsDNA. We highlight the spin-filtering capabilities of seven representative DNA origami-based chiral monolayers, demonstrating a maximal one-order-of-magnitude increase in spin-filtering efficiency per unit area compared with conventional dsDNA chiral monolayers. Intriguingly, our findings reveal that the higher-order tertiary chiral structure of twisted DNA origami further enhances the spin-filtering efficiency. This work paves the way for the rational design of DNA chiral monolayers.

Potassium-sulfur batteries attract tremendous attention as high-energy and low-cost energy storage system, but achieving high utilization and long-term cycling of sulfur remains challenging. Here we show a strategy of optimizing potassium polysulfides for building high-performance potassium-sulfur batteries. We design the composite of tungsten single atom and tungsten carbide possessing potassium polysulfide migration/conversion bi-functionality by theoretical screening. We create two ligand environments for tungsten in the metal-organic framework, which respectively transmute into tungsten single atom and tungsten carbide nanocrystals during pyrolysis. Tungsten carbide provide catalytic sites for potassium polysulfides conversion, while tungsten single atoms facilitate sulfides migration thereby significantly alleviating the insulating sulfides accumulation and the associated catalytic poisoning. Resultantly, highly efficient potassium-sulfur electrochemistry is achieved under high-rate and long-cycling conditions. The batteries deliver 89.8% sulfur utilization (1504 mAh g -1 ), superior rate capability (1059 mAh g -1 at 1675 mA g -1 ) and long lifespan of 200 cycles at 25 °C. These advances enlighten direction for future KSBs development., (© 2024. The Author(s).)

Aqueous zinc ion batteries (ZIBs), especially those with self-charging properties, have been promisingly developed in recent years. Yet, most inorganic materials feature high redox potential, which limit their development in the self-charging field. To achieve this target, by pre-embedding potassium ions into δ-MnO 2 to reduce the energy barrier in oxygen adsorption, the first application of MnO 2 in self-charging ZIBs is realized. The design features a facile two-electrode configuration with no excessively complex component to allow for energy storage and conversion. Due to the voltage difference between the oxygen in the air and the discharge products, a redox reaction can be carried out spontaneously to realize the self-charging process. After the chemical self-charging process, the Zn-K 0.37 MnO 2 ·0.54H 2 O/C cell achieves an open circuit voltage of around 1.42 V and a discharge capacity of 201 mAh g -1 , reflecting the promising self-charging capability. Besides, the chemically self-charging ZIBs operate well in multiple modes of constant current charge/discharge/chemical charging. And decent cycling capability can also be achieved at extreme temperatures and high mass loading. This work promotes the development of ZIBs and further broadens the application of inorganic metal oxides in the self-charging systems., (© 2023 Wiley-VCH GmbH.)

It is vitally important to develop highly active, robust and low-cost transition metal-based electrocatalysts for overall water splitting in neutral solution especially at large current density. In this work, amorphous Mo-doped NiS 0.5 Se 0.5 nanosheets@crystalline NiS 0.5 Se 0.5 nanorods (Am-Mo-NiS 0.5 Se 0.5 ) was synthesized using a facil one-step strategy. In phosphate buffer saline solution, the Am-Mo-NiS 0.5 Se 0.5 shows tiny overpotentials of 48 and 209 mV for hydrogen evolution reaction (HER), 238 and 514 mV for oxygen evolution reaction (OER) at 10 and 1000 mA cm -2 , respectively. Moreover, Am-Mo-NiS 0.5 Se 0.5 delivers excellent stability for at least 300 h without obvious degradation. Theoretical calculations revealed that the Ni sites in the defect-rich amorphous structure of Am-Mo-NiS 0.5 Se 0.5 owns higher electron state density and strengthened the binding energy of H 2 O, which will optimize H adsorption/desorption energy barriers and reduce the adsorption energy of OER determining step., (© 2022 Wiley-VCH GmbH.)

The state-of-the-art active hydrogen evolution reaction (HER) catalysts in acid electrolytes generally lose considerable catalytic performance in alkaline electrolytes mainly due to the additional water dissociation step. Designing composite materials is an effective strategy to accelerate alkaline water electrolysis by optimizing the electronic structure of materials. Here, different phases of Co(OH) 2 -supported Ru clusters (α/β-Co(OH) 2 @Ru) are prepared for enabling a highly efficient electrocatalytic HER performance in alkaline solution. The prepared α-Co(OH) 2 nanosheets facilitate the loading of uniform and high-density Ru clusters and the formed highly active RuOCo bonds at the interface. The synergistic interaction endows the hybrid catalyst with low overpotential of 33 mV at 10 mA cm -2 . Moreover, the homemade anion exchange membrane water electrolysis cell based on α-Co(OH) 2 @Ru affords a cell voltage of 2 V to drive a current density of 270 mA cm -2 and performs stably during continuous operation for over 100 h. Density functional theory calculations demonstrate that active RuOCo bonds in α-Co(OH) 2 @Ru optimize the energy barriers for H 2 O dissociation and OH - desorption to facilitate the Volmer reaction step. This work offers a strategy for designing interfacial chemical bonds for high electrocatalytic activity., (© 2023 Wiley-VCH GmbH.)

Zinc-nickel batteries are promising competitors for next-generation power supply due to their benefits of high safety, high working voltage, and attractive rate performance. However, their practical applications are plagued by their poor cycling performance, stemming from uneven redistribution of zinc during cycling that results in dendrite formation and shape changes of the electrode. In this work, mesoporous Ti 4 O 7 microspheres are prepared and are employed as additives of a zinc anode. Notably, the presence of mesopores provides abundant chemisorption sites for Zn(OH) 4 2- ions, inhibiting severe zinc redistribution in the electrode. Moreover, due to the good electrical conductivity and mesopores that serve as ion diffusion channels, the reaction reactivity and reversibility of the zinc electrode are greatly facilitated. As a result, the fabricated zinc-nickel battery with mesoporous Ti 4 O 7 additives (ms-Ti 4 O 7 ) exhibits an enhanced discharge capacity and a significantly prolonged cycling life. Even at a current of 10 A (∼138 mA cm -2 ), the ms-Ti 4 O 7 -modified anode demonstrates stable operation for longer than 718 h (700 cycles) with a discharge voltage of 1.2 V, which is much longer than those of a ZnO anode (192 h, 117 cycles) and a Ti 4 O 7 -particle (p-Ti 4 O 7 )-modified battery (590 h, 443 cycles). Furthermore, due to the anchoring effect for Zn(OH) 4 2- and the uniform electric field, the effect of mesoporous Ti 4 O 7 on inhibiting dendrite formation and shape change of the zinc electrode is highlighted.

Photoreduction of CO 2 to C 2+ solar fuel is a promising carbon-neutral technology for renewable energy. This strategy is challenged by its low productivity due to low efficiency in multielectron utilization and slow C-C coupling kinetics. This work reports a dual-metal photocatalyst consisting of atomically dispersed indium and copper anchored on polymeric carbon nitride (InCu/PCN), on which the photoreduction of CO 2 delivered an excellent ethanol production rate of 28.5 μmol g -1  h -1 with a high selectivity of 92 %. Coupled experimental investigation and DFT calculations reveal the following mechanisms underpinning the high performance of this catalyst. Essentially, the In-Cu interaction enhances the charge separation by accelerating charge transfer from PCN to the metal sites. Indium also transfers electrons to neighboring copper via Cu-N-In bridges, increasing the electron density of copper active sites. Furthermore, In-Cu dual-metal sites promote the adsorption of *CO intermediates and lower the energy barrier of C-C coupling., (© 2022 Wiley-VCH GmbH.)

Converting CO 2 into value-added chemicals and fuels is one of the promising approaches to alleviate CO 2 emissions, reduce the dependence on nonrenewable energy resources, and minimize the negative environmental effect of fossil fuels. This work used density functional theory (DFT) calculations combined with microkinetic modeling to provide fundamental insight into the mechanisms of CO 2 hydrogenation to hydrocarbons over the iron carbide catalyst, with a focus on understanding the energetically favorable pathways and kinetic controlling factors for selective hydrocarbon production. The crystal orbital Hamiltonian population analysis demonstrated that the transition states associated with O-H bond formation steps within the path are less stable than those of C-H bond formation, accounting for the observed higher barriers in O-H bond formation from DFT. Energetically favorable pathways for CO 2 hydrogenation to CH 4 and C 2 H 4 products were identified which go through an HCOO intermediate, while the CH* species was found to be the key C 1 intermediate over χ-Fe 5 C 2 (510). The microkinetic modeling results showed that the relative selectivity to CH 4 is higher than C 2 H 4 in CO 2 hydrogenation, but the trend is opposite under CO hydrogenation conditions. The major impact on C 2 hydrocarbon production is attributed to the high surface coverage of O* from CO 2 conversion, which occupies crucial active sites and impedes C-C couplings to C 2 species over χ-Fe 5 C 2 (510). The coexistence of iron oxide and carbide phases was proposed and the interfacial sites created between the two phases impact CO 2 surface chemistry. Adding potassium into the Fe 5 C 2 catalyst accelerates O* removal from the carbide surface, enhances the stability of the iron carbide catalyst, thus, promotes C-C couplings to hydrocarbons.

Facilitating the efficient activation of N 2 molecules and inhibiting the competing hydrogen evolution reaction remain a challenge in the nitrogen reduction reaction (NRR). A heteroatom doping strategy is an effective way to optimize the energy barrier during the NRR process to improve the catalytic efficiency. Herein, we report Ni-doped Mo 2 C anchored on graphitized porous conductive carbon for regulating the electronic structure and catalytic properties of electrocatalysts toward NRR. Benefiting from the porous structure and graphitization features of the carbon matrix, more active sites and high electronic conductivity were achieved. Meanwhile, with the doping of Ni atoms, the electronic configuration near the Ni-Mo active sites was optimized and the adsorption of N 2 on them was also promoted due to the increased electron transfer. Moreover, the lowered energy barrier of the NRR process and the suppressed hydrogen adsorption on the active site all resulted in the high catalytic activity and selectivity of the catalyst. Therefore, a high NH 3 yield rate of 46.49 μg h -1 mg -1 and a faradic efficiency of 29.05% were achieved. This work not only validates the important role of heteroatom doping on the regulation of NRR catalytic activity but also provides a promising avenue for the green synthesis of NH 3 .

Efficient electroreduction of CO 2 to multi-carbon products is a challenging reaction because of the high energy barriers for CO 2 activation and C-C coupling, which can be tuned by designing the metal centers and coordination environments of catalysts. Here, we design single atom copper encapsulated on N-doped porous carbon (Cu-SA/NPC) catalysts for reducing CO 2 to multi-carbon products. Acetone is identified as the major product with a Faradaic efficiency of 36.7% and a production rate of 336.1 μg h -1 . Density functional theory (DFT) calculations reveal that the coordination of Cu with four pyrrole-N atoms is the main active site and reduces the reaction free energies required for CO 2 activation and C-C coupling. The energetically favorable pathways for CH 3 COCH 3 production from CO 2 reduction are proposed and the origin of selective acetone formation on Cu-SA/NPC is clarified. This work provides insight into the rational design of efficient electrocatalysts for reducing CO 2 to multi-carbon products.

In this study, functionalized composite catalysts, namely, ILs (ILX/(ZnBr 2 ) 2 ), with hydroxyl, carboxyl and amino groups immobilized on a molecular sieve (MCM-22) support were synthesized with the help of a silane coupling agent, 3-chloropropyltriethoxysilane (CPTES). Cycloaddition of CO 2 and propylene oxide (PO) was carried out in a fixed bed reactor. The results show that MCM-22-CPTES-[AeMIM][Zn 2 Br 5 ] demonstrates the best catalytic properties for this reaction. A high selectivity and yield of propylene carbonate (PC) could be reached at 130 °C under a CO 2 pressure of 2.0 MPa, with a LHSV of 0.75 h -1 and a molar ratio of CO 2 /PO of 3 : 1. The yield stabilized at 61.6% after 50 h in the fixed bed reactor., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Catalytic conversion of CO2 including hydrogenation has attracted great attention as a method for chemical fixation of CO2 in combination with other techniques such as CO2 capture and storage. Potassium is a well-known promotor for many industrial catalytic processes such as in Fischer-Tropsch synthesis. In this work, we performed density functional theory (DFT) calculations to investigate the effect of potassium on the adsorption, activation, and dissociation of CO2 over Fe(100), Fe5C2(510) and Fe3O4(111) surfaces. The function of K was analyzed in terms of electronic interactions between co-adsorbed CO2 and K-surfaces which showed conspicuous promotion in the presence of K of the adsorption and activation of CO2. The adsorption strength of CO2 on these surfaces ranks as oct2-Fe3O4(111) > Fe(100) > Fe5C2(510). Generally, we observed a direct proportional correlation between the adsorption strength and the charges on the adsorbates. Adding K on the catalyst surface also reduces the kinetic barrier for CO2 dissociation. CO2 dissociation is more facile to occur on Fe(100) and Fe5C2(510) in the presence of K whereas the Fe3O4(111) surfaces impede CO2 dissociation regardless of the existence of K. Instead, a stable CO3- species is formed upon CO2 adsorption on Fe3O4(111) which will be directly hydrogenated when sufficient H* are available on the surface. Our results highlight the origin of the promotion effect of potassium and provide insight for the future design of K-promoted Fe-based catalysts for CO2 hydrogenation.

CO 2 hydrogenation to hydrocarbons is a promising way of making waste to wealth and energy storage, which also solves the environmental and energy issues caused by CO 2 emissions. Much efforts and research are aimed at the conversion of CO 2 via hydrogenation to various value-added hydrocarbons, such as CH 4 , lower olefins, gasoline, or long-chain hydrocarbons catalyzed by different catalysts with various mechanisms. This review provides an overview of advances in CO 2 hydrogenation to hydrocarbons that have been achieved recently in terms of catalyst design, catalytic performance and reaction mechanism from both experiments and density functional theory calculations. In addition, the factors influencing the performance of catalysts and the first C-C coupling mechanism through different routes are also revealed. The fundamental factor for product selectivity is the surface H/C ratio adjusted by active metals, supports and promoters. Furthermore, the technical and application challenges of CO 2 conversion into useful fuels/chemicals are also summarized. To meet these challenges, future research directions are proposed in this review., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)