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Zn-TCPP(M)/MOF (metal–organic framework) hybrids were synthesized. The H 2 yield of NM@Zn-T(Cu)-3 was 620.56 µmol g−1, which was 10.64 times and 3.8 times greater than Zn-TCPP(Cu) and NH 2 -MIL-125, respectively. [Display omitted] Photosensitizers are highly desirable due to their many applications. Photosensitizers play an important role in photocatalysis. However, conventional photosensitizers are not conducive to recycling. The proximity of the photosensitizing dye to the corresponding carrier is important in dye sensitization and in enhancing photocatalytic performance; however, most photosensitizers exhibit weak interactions with carriers. The transition of the photosensitizer from the molecule to the crystalline state enhances the stability of the photocatalyst and improves photocatalytic performance. In this study, MOF (metal–organic framework) @Zn-TCPP(M) hybrids were synthesized. The H 2 yield of NM@Zn-T(Cu)-3 was 620.56 µmol g−1 (4 h), which was 10.64 times and 3.80 times greater than Zn-TCPP(Cu) and NH 2 -MIL-125, respectively. The results revealed that the modification of the MOF with Zn-TCPP(M) altered the charge-transfer capability, and thus improved photocatalytic activity. This study reports a novel strategy to enhance the photocatalytic performance of Metal-Organic Framework using Zn-TCPP(M). [ABSTRACT FROM AUTHOR]

Water splitting based on first‐row transition metal (3d) photocatalysts is a cost‐effective technology for the conversion of abundant solar energy into useful energy on a large scale. The catalytic core of photosynthetic enzymes is a cubic CaMn4O5 cluster. Illuminated by natural photosynthesis, artificial solar water splitting photocatalysts composed of metal clusters are now being designed and tested. Ideally, such photocatalysts composed of atomically precise metal clusters with regular crystal structures are promising model catalysts that can be used to study structure–performance relationships. Recent advances based on metal cluster designs have improved our understanding of photoinduced charge separation and catalytic water redox reactions. This Minireview summarizes the recent advances in 3d metal cluster photocatalysts with well‐defined structures for photocatalytic water splitting and focuses on different clusters with tunable structures that are capable of achieving better photocatalytic properties. [ABSTRACT FROM AUTHOR]

Heterometallic lanthanide–transition‐metal (4f–3d) clusters with well‐defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f–3d clusters Ln52Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52Ni56 were exchanged by the Cd2+ to form Ln52Ni56−xCdx/CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52Ni56−xCdx cluster enable high visible‐light‐driven hydrogen evolution at 25 353 μmol h−1 g−1. This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f–3d clusters on semiconductor materials. Assembling lanthanide–transition‐metal (4f–3d) clusters Ln52Ni56 (Ln=Eu, Pr, Nd and Gd) onto CdS composites achieved enhanced photocatalytic H2 production. Some Ni2+ ions in the clusters were exchanged by Cd2+ to form Ln52Ni56−xCdx/CdS composites. An Eu52Ni56−xCdx/CdS species shows the highest activity of 25 353 μmol h−1 g−1 and an apparent quantum efficiency of 42.4 %. [ABSTRACT FROM AUTHOR]

Heterometallic lanthanide–transition‐metal (4f–3d) clusters with well‐defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f–3d clusters Ln52Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52Ni56 were exchanged by the Cd2+ to form Ln52Ni56−xCdx/CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52Ni56−xCdx cluster enable high visible‐light‐driven hydrogen evolution at 25 353 μmol h−1 g−1. This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f–3d clusters on semiconductor materials. [ABSTRACT FROM AUTHOR]

In this study, a novel ternary hybrid CdS/SiO 2 /TiO 2 film was proposed as the phonoanode for the photocatalytic fuel cell. The samples were characterized by X-ray diffraction, scanning electron microscopy and UV–vis absorption. The photoelectrochemical activity of the ternary hybrid electrode was characterized by the photocurrent-time transient response, linear sweep voltammetry and electrochemical impedance spectroscopy. It was shown that CdS/SiO 2 /TiO 2 yielded much higher photoelectrochemical activity than CdS/TiO 2 and bare TiO 2 did. The photoanode with CdS/SiO 2 /TiO 2 showed the highest photocurrent density of 4.6 mA cm −2 , exhibiting a 40% improvement over the conventional CdS/TiO 2 photoanode. The roles of SiO 2 and CdS in such a ternary configuration were elaborated. It was demonstrated that CdS could act as an excellent visible light captaturer to generate photo-induced charge carriers, and SiO 2 as a passivation layer to suppress the interfacial recombination of electrons and holes. Moreover, SiO 2 could allow for more CdS to be deposited at the photoanode owing to its high adsorption capacity. In addition, the effects of the SiO 2 content and the SILAR cycle time on the performance of the CdS/SiO 2 /TiO 2 photoanode were investigated. An optimal SiO 2 content of 10% could yield the best performance. Increasing the SILAR cycle time could improve the photoelectrochemical activity. [ABSTRACT FROM AUTHOR]

In this work, a membrane electrode assembled photoelectrochemical cell (PEC) is developed for the electricity generation by degrading the organic compounds. The photocatalyst is prepared by the incorporation of mesoporous silica SBA-15 into TiO 2 and the photosensitization of CdS-ZnS to enhance the photoanode performance, while the cathode employs the air-breathing mode to enhance the oxygen transport. The experimental results show that the developed PEC exhibits good photoresponse to the illumination and the appropriate SBA-15 mass ratio in the photoanode enables the enhancement of the performance. It is also shown that the developed PEC yields better performance in the alkaline environment than that in the neutral environment. Increasing the KOH concentration can improve the cell performance. There exist optimal liquid flow rate and organics concentration leading to the best performance. Besides, it is found that increasing the light intensity can generate more electron-hole pairs and thus enhance the cell performance. These results are helpful for optimizing the design. [ABSTRACT FROM AUTHOR]

The Bi 2 WO 6 /α-Fe 2 O 3 composite photocatalyst was synthesized by using goethite as a precursor through hydrothermal-calcination method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-Vis reflection spectrometer (DRS), X-ray photoelectron spectroscopy (XPS) and N 2 adsorption-desorption measurement (BET). These results indicated that the self-made composite photocatalysts had excellent catalytic performance of degradation of gaseous benzene. When benzene initial concentration at 50 mg/m 3 , over the α-FeOOH/Bi 2 WO 6 with molar mass of 0.8:1, calcined at 350 °C for 2 h and the pH of precursor solution was 3, the benzene degradation rate reached 71.9% and the mineralization efficiency reached 67.7% after 220 min UV irradiation, respectively. The h + and O 2 − generated in the photocatalytic system should be played a pivotal role for the enhanced photodegradation performance of gaseous benzene. [ABSTRACT FROM AUTHOR]

In this work, a novel photoanode with a cascading gradient pore microstructure is proposed to enhance photoelectrochemical and photocatalytic activities, which consists of a nanocrystalline TiO 2 layer synthesized by the sol–gel method, a microporous layer, and a macroporous layer formed by adding PEG and PMMA as the template, respectively. The gradient pore microstructure can not only enhance the mass and photon transfer and improve the light utilization, but also increase the electrical conductivity and restrain the recombination of photoexcited electron–hole pairs. Furthermore, the cascading design helps to establish tighter interparticle connections between layers. Because of these merits, it has been found that the cascading gradient pore microstructured photoanode exhibited a 63% improvement over the conventional photoanode in terms of photoelectrochemical activity. This new design also enhanced the photocatalytic activity, leading to a much higher methylene blue degradation efficiency (76.7%) than that of conventional photoanodes (62.5%). The effect of the PMMA/TiO 2 ratio on the structure and performance of the proposed photoanode was also investigated. The highest performance was achieved with a PMMA/TiO 2 ratio of 1:1. The obtained results establish a new avenue for designing the photoanodes of photoelectrochemical systems. [ABSTRACT FROM AUTHOR]

The in situ synthesis of ZnO-embedded Zn1−xCdxS/CdS heterostructure nanocrystals was achieved by using a simple surfactant-free hydrothermal route. The morphology and the exposed active site content of Zn1−xCdxS/CdS could be facilely modulated by varying the particle size of ZnS precursors, and the heterostructure with the smallest particle size showed the highest photocatalytic activity of 22.99 mmol h−1 g−1 in Na2S + Na2SO3 solution. Furthermore, the in situ embedding of the ZnO cocatalyst on the Zn1−xCdxS/CdS heterostructure dramatically improved its photocatalytic activity to 84.17 mmol h−1 g−1, which is 765 times higher than that of CdS prepared by a hydrothermal method. More significantly, the ZnO-embedded Zn1−xCdxS/CdS heterostructure gave a considerable H2 production rate even in the absence of hole scavengers, whereas the bare Zn1−xCdxS/CdS exhibited no hydrogen evolution, and it showed very competitive photocatalytic activity in methanol in comparison with that in Na2S + Na2SO3 solution under similar alkaline circumstances. These investigations indicate that the existence of the ZnO cocatalyst in the heterostructure could not only effectively improve the photocatalytic activity by suppressing the recombination of charge carriers and acting as a photocatalytic reaction site, but also make it possible to adopt methanol as the sacrificial reagent for sulfide photocatalysts. [ABSTRACT FROM AUTHOR]

PDMS (Polydimethylsiloxane) is a typical material used to fabricate optofluidic microreactors for photocatalytic water splitting application. However, conventional direct catalyst coating methods are unable to load catalysts firmly and uniformly on the PDMS substrate, which results in weak bond between the catalysts and substrate and thus poor durability and performance. To resolve this problem, a new casting-transfer method was proposed for loading catalysts on the PDMS substrate to fabricate the optofluidic microreactor in this work. By performing the tape testing and long-term testing, it was shown that the optofluidic microreactor fabricated by the new method exhibited critically high durability as compared to the conventional one. The hydrogen production rate was also higher than the conventionally fabricated microreactor. In addition, it was found that the optofluidic microreactor with the micro-grooved structure yielded higher hydrogen production rate than did the conventional planar optofluidic microreactor as a result of enhanced mass transport and reaction area. This method creates a new avenue to fabricate the PDMS based microreactors with high durability. [ABSTRACT FROM AUTHOR]

Abstract: A new polymorph telluridoindate [In(en)3][In5Te9(en)2] (denoted as β-type, en=ethylenediamine) has been solvothermally synthesized and characterized. The crystal data for the β-type are listed as follows: monoclinic, space group Cc (No. 9), a =11.642(2), b =20.421(4), c =17.577(4)Å, β =92.20(3)°, V =4175.7(14)Å3, Z=4. The β-type contains organic-decorated [In4Te9(en)]6− supertetrahedral cluster and [InTe3(en)]3− tetrahedron, which are interconnected to form an organic-decorated 2-D telluridoindate layer of [In5Te9(en)2 3−]n with 9-membered rings. Two relevant conformers of telluridoindates are compared with each other. The β-type indicates absorption edge at 2.23eV and exhibits photocatalytic activity for degradation of methyl orange (MO). [Copyright &y& Elsevier]

[Display omitted] • Interfacial complexation of Fe3+ and Bi 2 MoO 6 is established in the presence of PDS. • The complexation between Fe3+ and Bi 2 MoO 6 accelerates the Fe3+/Fe2+ cycle. • Efficient organic contaminants degradation is achieved by Bi 2 MoO 6 /Fe3+/PDS/Vis system. • The Fe3+/Fe2+ redox cycle is employed to promote the continuous activation of PDS. To address the observed decrease in efficiency during Fe2+-mediated persulfate (PDS) activation caused by slow electron transfer rates and challenges in cycling between Fe3+/Fe2+ states, we devised a strategy to establish interfacial complexation between Fe3+ and Bi 2 MoO 6 in the presence of PDS. The proposed approach facilitates more efficient capture of photogenerated electrons, thereby accelerating the rate-limiting reduction process of the Fe3+/Fe2+ cycle under visible light irradiation and promoting PDS activation. The Bi 2 MoO 6 /Fe3+/PDS/Vis system demonstrates complete degradation of organic pollutants, including Atrazine (ATZ), carbamazepine (CBZ), bisphenol A (BPA), and 2,4-dichlorophenol (DCP) at a concentration of 10 mg/L within a rapid reaction time of 30 min. Radical scavenging experiments and electron paramagnetic resonance spectra (EPR) confirm that the sulfate radical (•SO 4 −) is the dominant species responsible for organic contaminant degradation. The real-time conversion process between Fe3+ and Fe2+ was monitored by observing changes in iron species forms and concentrations within the reaction system. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy verify the formation of a complexation between Fe3+ and Bi 2 MoO 6 , facilitating anchoring of Fe3+ onto material surface. Based on these findings, we propose a reliable mechanism for the activation reaction. This work presents a promising heterogeneous PDS activation method based on Fe3+/Fe2+ cycle for water treatment. [ABSTRACT FROM AUTHOR]

Inspired by natural photosynthesis, the design of novel Z-scheme photocatalytic systems holds great promise for improving photocatalytic hydrogen production performance. Here, we constructed a Z-scheme heterojunction to effectively improve the charge separation of TiO 2 /ZnIn 2 S 4 , with the N-doped C layer acting as an electron bridge. The T@NC-A/ZIS-72 heterojunctions demonstrated hydrogen production activity approximately 12.1 and 97.9 times higher than those of ZnIn 2 S 4 and TiO 2 @NC-A, respectively. The excellent electron migration ability of the carbon layer accelerated the photocatalytic hydrogen production performance. Our design introduces a component to provide a dedicated charge transport pathway, overcoming the inherent properties of the material and providing a new perspective for enhancing photocatalytic performance. [ABSTRACT FROM AUTHOR]

BiOBr ultrathin nanosheets with the thickness of 3–4 nm were prepared via an ionic liquid ([C 16 mim]Br) assisted mechanochemical synthesis method at ambient temperature for the first time. Remarkably improved photocatalytic activity for BPA and TC degradation demonstrating ionic liquid assisted ball milling method brings out a promising research prospect for the synthesis of ultrathin nanosheet with preeminent photocatalytic performance. Ultrathin BiOBr nanosheets have been prepared via an ionic liquid induced mechanochemical synthesis method at ambient temperature for the first time using 1-hexadecyl-3-methy-limidazolium bromine ([C 16 mim]Br). Transmission electron microscope and atomic force microscope images show that the ultrathin BiOBr nanosheets possessed an average diameter of approximately 200–300 nm with a thickness of 3–4 nm. For comparison, KBr was selected as Br source for the preparation of BiOBr nanosheets and the experimental results demonstrate that the ionic liquid and mechanical ball milling method had a significant impact on the fabrication of nanosheet structures. Compared with the as-prepared control samples, the ultrathin BiOBr nanosheet photocatalyst exhibited significantly increased photocatalytic performance for the removal of organic pollutants. A possible mechanism for this enhanced activity was proposed based on the shorter diffusion distance for charge transfer provided by the ultrathin nanosheet structure, which inhibits the recombination of photogenerated charge carriers. This work not only opens up a possible pathway for the large-scale industrial preparation of BiOX (X = Cl, Br, I) with superior photocatalytic activity, but also provides new insight into environmental restoration and energy conversion. [ABSTRACT FROM AUTHOR]

In this work, a photocatalytic fuel cell (PFC) with membrane electrode assembly (MEA) structure was designed for simultaneous organic compounds degradation and electricity generation. For the photoanode, the TiO 2 with the quantum-dot sensitization by CdS-ZnS was used to broaden the absorption spectrum to visible light. For the cathode, an air-breathing mode was utilized to enhance the oxygen transport. The performance of the developed PFC was evaluated under different operation conditions, including the light intensity, liquid flow rate, concentrations of electrolyte and organics. Results indicated that the designed PFC could yield good performance. The increase of the light intensity and electrolyte concentration could improve the PFC performance. It is also found that when the flow rate was increased, the PFC performance dropped down in the testing range. Too high organics concentration led to the decrease of the PFC performance. [ABSTRACT FROM AUTHOR]

Semiconductor photocatalytic performances can be modulated through morphology modification. Herein porous hierarchical BiOBr microspheres (BiOBr-MS) of ~3 μm was firstly self-assembled without the assistance of a template via a facile solvothermal synthesis in triethylene glycol (TEG) at 150 °C for 3 h. KBrO3 was exploited as a bromine source, which slowly provided bromide ions upon reduction in TEG and controlled the growth and self-assembly of primary BiOBr nanoplates. The addition of PVP during solvothermal synthesis of BiOBr-MS reduced the particle size by about three-fold to generate BiOBr sub-microspheres (BiOBr-sMS) of <1 μm. BiOBr-sMS exhibited significantly higher photocatalytic activity than BiOBr-MS for aerobic photooxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) under simulated sunlight irradiation (conversions of BzOH (50 mM) over BiOBr-sMS and BiOBr-MS were, respectively, 51.3% and 29.6% with 100% selectivity to BzH after Xenon illumination for 2 h at 25 °C). The photogenerated holes and ·O2− were found to be main reactive species for the BzOH oxidation over BiOBr spheres by scavenging tests and spin-trapping EPR spectra. The higher photocatalytic activity of BiOBr-sMS was attributed to its more open hierarchical structure, efficient charge separation, more negative conduction-band position and the generation of larger amounts of ·O2−. [ABSTRACT FROM AUTHOR]

[Display omitted] Solar-driven photocatalytic H 2 evolution could tackle the issue of fossil fuels-triggered greenhouse gas emission with sustainable clean energy. However, splitting water into hydrogen with high performance by a single semiconductor is challenging because of the poor charge separation efficiency. Herein, a novel ternary Cu@TiO 2 -Cu 2 O hybrid photocatalyst with multiple charge transfer channels has been designed for efficient solar-to-hydrogen evolution. Indeed, the ternary Cu@TiO 2 -Cu 2 O hybrid by coupling Cu@TiO 2 with Cu 2 O nanoparticles shows highly-efficient photocatalytic hydrogen generation with rate of 12000.6 μmol·g−1·h−1, which is 4.4, 2.1, and 1.9 times higher than the pure TiO 2 (2728.8 μmol·g−1·h−1), binary Cu@TiO 2 (5595.5 μmol·g−1·h−1), and TiO 2 -Cu 2 O (6076.8 μmol·g−1·h−1) composite, respectively. In such a Cu@TiO 2 -Cu 2 O hybrid, the formed internal electric field in the TiO 2 -Cu 2 O p-n junction allows the electrons in Cu 2 O to migrate to TiO 2 , while the electrons in the CB of TiO 2 could flow into Cu via the Schottky junction at the Cu@TiO 2 interface. In this regard, a multiple charge transfer is achieved between the Cu@TiO 2 and Cu 2 O, which facilitates promoted charge separation and results in the construction of electron-accumulated center (Cu) and hole-enriched surface (Cu 2 O). This p-n/Schottky junctions with steered charge transfer assists the hydrogen production upon the Cu@TiO 2 -Cu 2 O ternary photocatalyst. [ABSTRACT FROM AUTHOR]

Photocatalytic fuel cell is a promising technology for simultaneous wastewater treatment and electricity generation. To more directionally improve the cell performance, a deep understanding of respective photoanode and cathode performances is of vital importance. In this work, therefore, a high-performance photocatalytic fuel cell with a visible-light responsive photoanode and an air-breathing cathode was developed to gain insight into each electrode potential characteristics. The potentials of each electrode were measured under different operational parameters. Experimental results showed that too low fuel concentration led to a serious mass transfer limitation at the photoanode and too high fuel concentration led to a low ionic conductivity, both of which deteriorated the cell performance. Therefore, there existed an optimum fuel concentration to achieve the best cell performance. It was also shown that an increase in the electrolyte concentration markedly improved both the photoanode and cathode performances due to enhanced reaction rates and lowered internal resistance, thereby leading to the increased cell performance. In addition, it was demonstrated that the light intensity significantly affected the photoanode potential and increasing the light intensity boosted the cell performance. The results obtained in this work provide the guidance for improving the photocatalytic fuel cell performance in future applications. [ABSTRACT FROM AUTHOR]

As the development of the "golden waterway" for the Yangtze River and the formation of the Three Gorges Reservoir area, the inland river shipping of chemical is increasing in China. At the same time, the risk of chemical leak accident is on the rising. Recent years, photo-catalyst has attracted great interest in environmental pollution treating for its unique properties. In order to improve its ability in pollution degradation, different kinds of doped 2 are made in this work. Since the toxicity and transportation quantity, p-Xylene is researched as the aim chemical in this research. The influence of different catalyst, lighting time and reaction temperature to p-Xylene degradation rate are studied respectively in detail. [ABSTRACT FROM AUTHOR]

Semiconductor photocatalysis has long been regarded as a potential solution to tackle the energy and environmental challenges since the first discovery of water splitting by TiO2 almost 50 years ago. The past few years have seen a tremendous flurry of research interest in the modification of semiconductors because of their shortcomings in the aspects of solar harvesting, electron‐hole pairs separation, and utilization of photogenerated carriers. Among the various strategies, the introduction of metallic copper into the photocatalysis system can not only enhance the absorption of sunlight and the separation efficiency of photogenerated electrons and holes, but also increase the adsorption ability of substrate and the number of active sites, so as to realize the high solar to chemical energy conversion efficiency. This review focuses on the rational design of copper‐based composites and their applications in photoredox catalysis. First, the preparation methods of metallic copper‐containing composites are discussed. Then, the applications of different types of copper‐based composites in the photocatalytic removal of pollutants, splitting of water to hydrogen production, reduction of carbon dioxide, and conversion of organic matter are introduced. Finally, the opportunities and challenges in the design and synthesis of copper‐based composites and their applications in the photocatalysis are prospected. [ABSTRACT FROM AUTHOR]

With the massive consumption of fossil fuels, energy crisis and effectively reducing CO 2 to curb global warming have become urgent and severe problems in the world. Photocatalytic conversion of CO 2 technology which can convert CO 2 into combustible compounds by using solar energy can solve both of the problems mentioned above. However, the photocatalytic conversion of CO 2 exhibits too low efficiency, especially under visible light. So, in order to improve the photocatalytic efficiency, the composite photocatalysts of TiO 2 nanotube array (TNTA) sensitized by CdS/ZnS quantum dots (QDs) were successfully prepared by anodization method and successive ionic layer adsorption and reaction (SILAR) method in this work. And the composite photocatalysts exhibited a high performance for photocatalytic conversion of gas-phase CO 2 to methanol under visible light. X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscope (TEM), and X-ray photoelectric spectroscopy (XPS) were employed to characterize the ingredients and morphologies of the synthesized photocatalysts. And, UV–vis diffuse reflectance spectra (UV–Vis DRS) revealed that CdS/ZnS QDs enhanced the photo-absorption of composite photocatalyst in the visible light region. The main product methanol yield of CdS/ZnS-TNTA under visible light was 2.73 times that of bare TNTA when TNTA was treated by 10 SILAR cycles. Meanwhile, the product yield first increased before decreasing with the increase of the CO 2 flow rate. And the greatest product yield reached up to 255.49 nmol/(cm2-cat·h) with the increase of light intensity. The reaction mechanism was discussed in this paper. This high performance for photocatalytic reduction of CO 2 was primarily attributed to the CdS/ZnS QDs sensitization, which widens the response wavelength range of the catalyst to include visible light and partly inhibits the recombination of electron-hole pairs. [Display omitted] • TiO 2 nanotube array sensitized by CdS/ZnS was used for photoreduction of CO 2. • The best methanol yield reached 255.49 nmol/(cm2 cat ·h) under visible light. • Effects of CdS/ZnS contents, flow rates and light intensities were investigated. • The yield of CdS/ZnS-TNTA was 2.73 times that of bare TNTA. [ABSTRACT FROM AUTHOR]

Solar-driven reduction of CO 2 and H 2 O into fuels is a promising approach for addressing global warming and energy crisis. Herein, Cu+ doped W 18 O 49 nanowires were prepared by a facile solvothermal method and applied in photocatalytic reduction of CO 2. The composition and structure of pristine and Cu+ doped W 18 O 49 samples have been characterized. It was found that the morphology of W 18 O 49 nanowires was changed with increasing amounts of dopant. The photocatalytic CO 2 reduction activity of W 18 O 49 nanowires and the Cu+ doped W 18 O 49 samples were evaluated using H 2 O as reducing agent. The strategy of Cu+ doping not only could affect the band edge position and the surface wettability, but also influenced separation of the photogenerated electron-hole pairs. It was found that Cu+ doping could introduce oxygen vacancy and change the conduction edge to a more negative position for W 18 O 49 nanowires, which might be beneficial for the activation of CO 2 and promote the following CO 2 reduction. Furthermore, the higher separation efficiency of photogenerated electron-hole pairs with Cu+ doping could contribute to the CO 2 photoreduction enhancement. In addition, the Cu+ doped W 18 O 49 nanowires (Cu-W 18 O 49 -0.005) presented a relatively poor hydrophilic property, which might be beneficial for the adsorption of CO 2 molecules and contribute to its superior photocatalytic CO 2 reduction capability. [ABSTRACT FROM AUTHOR]

A photoactive MOF-based composite with simultaneously incorporated Ru-photosensitizer and Ni(II) molecular catalyst via a "ship-in-a-bottle" synthetic strategy, exhibits highly active, selective and robust, for photocatalytic CO 2 to CO conversion under visible-light illumination. Photocatalytic reduction of CO 2 to CO is a promising strategy for reducing atmospheric CO 2 levels and storing solar radiation as chemical energy. Here, we demonstrate that a molecular catalyst [NiII(bpet)(H 2 O) 2 ] successfully encapsulated into a highly robust and visible-light responsive metal–organic framework (Ru-UiO-67) to fabricate composite catalysts for photocatalytic CO 2 reduction. The composite Ni@Ru-UiO-67 photocatalysts show efficient visible-light-driven CO 2 reduction to CO with a TON of 581 and a selectivity of 99% after 20-h illumination, because of the facile electron transfer from Ru-photosensitizer to Ni(II) active sites in Ni@Ru-UiO-67 system. The mechanistic insights into photoreduction of CO 2 have been studied based on thermodynamical, electrochemical, and spectroscopic investigation, together with density functional theory (DFT) calculations. This work shows that encapsulating molecular catalyst into photoactive MOF highlights opportunities for designing efficient, stable and recyclable photocatalysts. [ABSTRACT FROM AUTHOR]

Graphical abstract Bi/Bi 3.64 Mo 0.36 O 6.55 heterostructure promotes the selective oxidation of glycerol to DHA under visible light irradiation via a dual-pathway photocatalytic reaction process involving photogenerated 1O 2 and holes. Highlights • Bi/Bi 3.64 Mo 0.36 O 6.55 heterostructure were prepared by a facile one-step solvothermal method. • The reduced energy gap, the enhanced spin-orbit coupling and the presence of oxygen vacancy in Bi/Bi3.64Mo0.36O6.55 heterostructure promoted the mass production of 1O2. • Dual reaction pathways induced by photogenerated 1O 2 and holes were formed over Bi/Bi 3.64 Mo 0.36 O 6.55 heterostructure. • The dual reaction-pathway process greatly promoted the selective oxidation of glycerol to DHA. Abstract Selective oxidation of glycerol to produce aimed high-value added products is of great importance in chemical industry. Photocatalytic oxidation provides a promising and green strategy for selective glycerol oxidation. In this work, we develop a Bi/Bi 3.64 Mo 0.36 O 6.55 heterostructure via a facile solvothermal method for the selective oxidation glycerol to 1, 3-dihydroxyacetone (DHA) in water under visible light irradiation. The excellent performance in activity and selectivity of Bi/Bi 3.64 Mo 0.36 O 6.55 heterostructure for DHA production is attributed to a dual-pathway photocatalytic reaction process. The mass production 1O 2 ascribed to the reduced energy gap (ΔE ST), the enhanced spin-orbit coupling (SOC) and the presence of oxygen vacancy is beneficial for the selective oxidation of glycerol to DHA. Simultaneously, the metallic bismuth in the heterostructure promotes the separation of photogenerated holes with efficient redox potential and facilitates the binding bismuth with ortho-hydroxyl in glycerol, thus enhancing the yield and selectivity of DHA production. This work provides a novel strategy and thorough understanding of the development of highly efficient bismuth-based photocatalyst for selective oxidation in organic reactions. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • ∼1 wt% of Fe doped BiOCl were successfully prepared at room temperature. • Fe doped BiOCl exhibits enhanced activity for H 2 O 2 activation. • A new energy level in the forbidding band of BiOCl is formed via Fe doping. • DFT calculation reveal that Fe in BiOCl lattice facilitate electron trapped by H 2 O 2. Abstract BiOCl hierarchical nanostructures with trace amount of Fe doping (∼1 wt%) have been successfully prepared via a facile one-step room temperature method, which exhibits enhanced photocatalytic activity for the degradation of methyl blue (MB) under visible light irradiation. It is found that the photocatalysis of the Fe-doped BiOCl undergoes a hydroxyl radicals dominated photo-Fenton process. XRD, XPS and EDS data reveals that the doped Fe ions exist in the lattice of BiOCl by replacing the Bi atoms. The presence of Fe not only extends the solar energy response of the material from 350 to 600 nm by creating a new energy level in the forbidden band of BiOCl, but also alters the chemical state of the surface, resulting in the electron flowing favorably to H 2 O 2 rather than oxygen molecular in aqueous solution. [ABSTRACT FROM AUTHOR]

Novel N-doped carbon quantum dots (N-CQDs) modified Bi 4 O 5 I 2 hollow nanotubes photocatalysts have been prepared for the first time. Bi 4 O 5 I 2 nanomaterials with hollow nanotube structure were designed to shorten the charge carriers’ migration distance from bulk phase to surface while the N-CQDs was modified to accelerate the surface charge transfer. Multiple characterization methods have been applied to explore the phase structure, elemental composition, optical absorption properties and photocatalytic performance of as-prepared N-CQDs/Bi 4 O 5 I 2 composites. The N-CQDs/Bi 4 O 5 I 2 -0.2 composite showed higher photocatalytic activity for the removal of bisphenol A than pure Bi 4 O 5 I 2 hollow nanotube under UV light, visible light, light above 580 nm, which exhibited the broad spectrum photocatalytic activity. ESR analysis demonstrated the N-CQDs modification can tune the concentration of reactive oxygen species (•OH and •O 2 − ). Combined with free radical trapping experiment results, hole, •OH and •O 2 − were demonstrated to be the main active species and synergistically promoted the enhancement of photocatalytic activity for N-CQDs/Bi 4 O 5 I 2 composite. [ABSTRACT FROM AUTHOR]

• Ag particles and oxygen vacancy are synchronistically embedded into potholed TiO 2. • Influence of Ag dosage on CO 2 photoreduction of TiO 2-x is studied. • Oxygen vacancy facilitates light harvesting, charge separation, and migration. • The Ag/TiO 2 Schottky effect accelerates formation of electron-enriched Ag center. • The oxygen vacancy and Schottky Ag/TiO 2 cooperatively promotes CO 2 photoreduction. Photocatalytic CO 2 reduction offers a potential to produce clean and renewable fuels as well as reduce massive emissions of CO 2 by utilizing solar energy. The inhibited charge recombination and fertile surface reactive sites play vital roles in determining the photocatalytic performance and products selectivity in CO 2 reduction reaction. Herein, the Ag/TiO 2-x hybrid by synchronistic introduction of oxygen vacancy and Ag nanoparticles into SiO 2 spheres-templated potholed TiO 2 assembly with nanoparticles is constructed for photocatalytic CO 2 conversion. The Schottky junction between oxygen vacancy TiO 2-x and Ag particles provides synergistic enhancement of solar light utilization, photo-induced charge separation and migration process, which is of significance in the promoted CO 2 photo-conversion. Indeed, the CH 4 yield of oxygen vacancy TiO 2-x (1.56 μmol/g/h) is more than 3 times as high as the TiO 2 (0.47 μmol/g/h), while the as-synthesized Ag/TiO 2-x hybrids show an enhancement of photocatalytic CO 2 reduction into CH 4 and CO. Among them, the Ag/TiO 2-x -10% hybrid has the best photocatalytic performance, and it shows significantly superior CH 4 (8.61 μmol/g/h) and CO (2.27 μmol/g/h) yields to that of pure TiO 2-x and TiO 2. [Display omitted] [ABSTRACT FROM AUTHOR]

We developed a facile in-situ growth method to construct amorphous-based Bi 2 S 3 /Bi 2 WO 6 heterostructures at room temperature. As demonstrated by HRTEM, XPS and EDX-mapping, amorphous state Bi 2 S 3 dispersed uniformly on the surface of crystalline Bi 2 WO 6 hollow spheres. The photocatalytic activities of prepared Bi 2 S 3 /Bi 2 WO 6 heterostructures were evaluated by the photodegradation of RhB and TC under visible light irradiation, indicating that the introduction of appropriate amorphous Bi 2 S 3 significantly improved the photocatalytic activity of Bi 2 WO 6 . The amorphous/crystalline contact in Bi 2 S 3 /Bi 2 WO 6 heterostructures played a crucial role in the enhancement of photocatalytic efficiency. Based on DRS, photoluminescence spectra, photocurrent intensity, electrochemical impedance spectroscopy and OCVD measurements, it was proposed that the enhanced performance could be ascribed to increased visible light utilization, promoted separation efficiency and prolonged life time of photogenerated electron-hole pairs by the introduction of amorphous Bi 2 S 3 . This work may provide new insights into the construction of amorphous-based composited heterostructures for improving photocatalytic activity. [ABSTRACT FROM AUTHOR]

Oxalic acid (OA), together with its ligand, appears in diverse biotic and abiotic processes in nature. However, the applications of the photochemical property of OA and its complexes in environmental purification are scarce. Herein, we reported a Fe single-atom catalyst with Fe-N 4 configuration supported on g-C 3 N 4 (Fe-CN) to activate OA for ultrahigh-efficiency removal of Cr(VI) under visible light irradiation through dual pathways: the photo-dissociation of [FeⅢ(C 2 O 4)]+ and the reaction between OA and photogenerated holes, achieving the generation of •CO 2 -. The introduction of Fe-N 4 favors the formation of configuration [FeⅢ(C 2 O 4)]+ and fabricates the electron transfer channel from catalyst to OA, further decreases the energy barriers of •CO 2 - generation, and thereafter efficiently facilitates the C-C cleavage for the generate of •CO 2 -. Meanwhile, the strong coordination interaction over Fe single atoms and N atoms could enhance the separation efficiency of photo-carriers and further promote the reduction activity. Under optimal conditions, Fe-CN showed a 5.1-fold increasement in photocatalytic kinetics contrast to pristine CN. The Fe-CN catalyst attached on fibrous membrane for treatment of flowing Cr(VI) wastewater exhibits 90% reduction efficiency over 10 h, which is expected to facilitate the practical application of the catalyst. The mechanism of OA activation with dual-pathway was unveiled by in-situ Fourier transform infrared spectra and theoretical calculations. This work provides an important guidance for the application of OA and its complexes to achieve the attenuation of toxic and harmful heavy metal in water restoration. [Display omitted] • The Fe single-atom catalyst was fabricated to OA activation for Cr(VI) detoxification. • The introduction of Fe-N 4 favors OA activation under visible irradiation through dual pathways. • The photo-dissociation of Fe-OA complex was unveiled based on the in-situ DRIFT and DFT calculations. • The Fe-N 4 active sites enhanced separation and migration of photocarriers, further accelerating the generation of •CO 2 -. • The combination of membrane technology with catalysis exhibits great stability, activity and retention effect. [ABSTRACT FROM AUTHOR]

TiO 2 -based heterogeneous photocatalysis has been widely considered as a promising technique for decontamination of water. Herein the hybrid of TiO 2 nanocrystals decorated Fe 2 O 3 nanoparticles was successfully synthesized via a mild hydrothermal method, derived from favorable titanium glycolate and water-soluble Fe II salt precursors. The composition and structure of the as-synthesized TiO 2 -Fe 2 O 3 hybrids were characterized by Powder X-ray diffraction (XRD), EDX mapping, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The photocatalytic activity was evaluated by the decomposition of Rhodamine B in an aqueous solution under visible-light ( λ > 420 nm). The results show that the TiO 2 -Fe 2 O 3 nanocomposite exhibits superior photocatalytic capability to the bare ones upon Rhodamine B degradation, owing to promoted photo-induced electrons and holes separation and migration on the basis of photoluminescence spectra, photocurrent measurements, and electrochemical impedance (EIS) spectroscopy. [ABSTRACT FROM AUTHOR]

TiO 2 @RGO, TiO 2 @CNTs, and TiO 2 @C (glucose carbon) hybrid composites exhibiting both excellent adsorption capability and photocatalytic activity having great potential in pollutant removal were synthesized and composition and nanostructure were determined in detail by state-of-the-art methods. These hybrid materials show enhanced visible light absorption and RhB-dye removal capability via adsorption and photocatalysis with their efficiency generally increasing with carbon content. TiO 2 @C with low carbon concentration promotes photocatalytic performance, while increasing carbon amount improves the adsorption efficiency. Among the three kinds of TiO 2 -carbon hybrids, TiO 2 @RGO with optimized RGO-content (2 wt.%) exhibited the best photocatalytic efficiency, attributed to efficient separation efficiency of injected electron and excited RhB with involving of RGO, while TiO 2 @C with 32 wt.% C showed the highest adsorption capability due to the most negative zeta potential and highest BET surface areas. This comparison study has revealed how TiO 2 @carbon material hybrids can be optimized for adsorption and photocatalytic toxin removal. [ABSTRACT FROM AUTHOR]

BiOBr hollow microspheres attached to few-layered molybdenum disulfide (MoS2) were prepared by an ethylene glycol (EG)-assisted microwave process in the presence of 1-hexadecyl-3-methylimidazolium bromine ([C16mim]Br). The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and UV-vis diffuse reflectance spectroscopy (DRS). During the reaction process, the ionic liquid [C16mim]Br acts as not only a solvent and Br source, but also as a microwave-absorbing agent and template for the fabrication of MoS2/BiOBr hollow microspheres. In addition, the photocatalytic activity of MoS2/BiOBr was evaluated for the degradation of ciprofloxacin (CIP) and Rhodamine B (RhB) under visible light irradiation. The results indicated that 0.2 wt% MoS2/BiOBr microspheres exhibit higher photocatalytic activity than BiOBr. A possible photocatalytic mechanism based on the relative band position of MoS2 and BiOBr was proposed. [ABSTRACT FROM AUTHOR]

Bismuth oxychloride (BiOCl) nanosheets with tunable thickness were synthesized via a facile solvothermal method. The obtained BiOCl products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption. It was found that the metal ions (Fe3+, Co2+ and Na+) played a significant role in modulating the thickness of two-dimensional (2D) BiOCl nanostructures. Compared with commercial P25 and commercial BiOCl, the as-prepared BiOCl nanosheets exhibited superior activity for photosensitization degradation of organic dyes upon visible light irradiation. Furthermore, the photosensitization degradation activities were strongly correlated with the thickness of BiOCl nanosheets. The thinner nanosheets demonstrated a relatively high activity for the degradation of Rhodamine B (RhB). The enhanced photosensitization activities were ascribed to its low electron injection barrier and high electron mobility on the surface of BiOCl nanosheets, which was confirmed by transient photocurrent responses and electron impedance spectra of the samples. [ABSTRACT FROM AUTHOR]

Sb-doped (BiO) 2 CO 3 nanoplates have been successfully fabricated via a facile hydrothermal method. XRD patterns, XPS spectra, SEM and TEM images demonstrated that doping with antimony (Sb) has no effect on the crystal phase, morphology and structure of (BiO) 2 CO 3 nanoplates. However, the red shift of diffraction peak in the 2θ range of 29–32° was observed, which could be attributed to the substitution of larger radius of Bi atoms by lower radius of Sb atoms resulting in the decrease of lattice parameters. The photocatalytic performance of Sb-doped (BiO) 2 CO 3 nanoplates was evaluated by the degradation of RhB upon visible light irradiation. It was found that the visible-light-induced photocatalytic activity of Sb-doped (BiO) 2 CO 3 nanoplates was significantly improved, which was mainly attributed to its enhanced surface area and electron transfer rate. It was proposed that RhB photodegradation proceeded through a photosensitization pathway upon visible light irradiation. [ABSTRACT FROM AUTHOR]

Abstract: Uniform 3D porous hierarchical ZnO microspheres were successfully prepared via a facile solvothermal method with the assistance of 2-(4-(2-hydroxyethyl)-1-piperazinyl) ethanesulfonic acid (HEPES). The product was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectroscopy (DRS) and nitrogen adsorption. HEPES acted as a directing agent in the assembling of hierarchical ZnO nanostructures. Besides, it was also found Triethylene glycol (TEG) with proper viscosity made contributions to the fabrication of porous ZnO microspheres. The synthesized hierarchical ZnO microspheres possessed largest BET surface area and ideal pore volume, as well as exhibited excellent photocatalytic activity for the photodegradation of methylene blue (MB) under UV light irradiation. [Copyright &y& Elsevier]

Abstract: Uniform bismuth hollow nanospheres with efficient Cr(VI) adsorption capacities were used to the photodegradation of highly toxic Cr(VI) for the first time, which exhibited outstanding visible-light photocatalytic abilities for the reduction of Cr(VI) to less toxic Cr(III). [Copyright &y& Elsevier]

Differentbismuth subcarbonate ((BiO)2CO3) hierarchicalnanostructures assembled by nanoplates or nanosheets have been successfullysynthesized via a simple hydrothermal route by properly monitoringexperimental conditions. The synergistic effect of citrate ions, urea,and solvent is of crucial importance for the controllable fabricationof (BiO)2CO3hierarchical nanostructures. Thecitrate ions play a key role in the assembly of 3D hierarchical nanostructures.The amount of urea could mediate the thickness of 2D structural units.The solvent could not only influence the thickness of the 2D structuralunit but also mediate the structure and assembly of hierarchical nanostructures.On the basis of experimental observation, a possible formation processof (BiO)2CO3hierarchical nanostructures waspreliminarily proposed. The photocatalytic performance of the as-prepared(BiO)2CO3hierarchical nanostructures was evaluatedby the photodegradation of Rhodamine B (RhB) upon UV light irradiation.It indicated that loose-packed flower-like (BiO)2CO3hierarchical nanostructures assembled by ultrathin nanosheetswith large BET surface area and narrow band gap displayed the bestphotocatalytic activity and favorable recycling characteristics. [ABSTRACT FROM AUTHOR]

Highlights: [•] Porous Er3+ doped β-Bi2O3 single crystalline nanosheet was synthesized using a simple template-free method. [•] The nanosheets selectively exposed reactive {001} facets as the main external surfaces. [•] The porous nanosheets exhibited an enhanced photoactivity. [•] The enhanced photocatalytic activity can be attributed to the exposed reactive {001} facets and the dopant. [Copyright &y& Elsevier]

Abstract: A facile polyol-mediated solvothermal method was developed to fabricate BiOCl hierarchical nanostructures (HNs) with controllable morphologies. The obtained BiOCl hierarchical nanostructures were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflection spectroscopy (DRS) and nitrogen adsorption. The BiOCl hierarchical nanostructures (HNs) with ellipsoid-like, sphere-like and flower-like morphologies were constructed of intercrossed nanoflakes or nanosheets. The polyols played significant roles in the fabrication of BiOCl hierarchical nanostructures, which functioned as solvents, reducing and morphology-directing agents. Importantly, the BiOCl hierarchical nanostructures exhibited excellent shape-dependent visible-light-driven photocatalytic activities for Rhodamine B (RhB) degradation, which was much higher than that of 2D BiOCl nanosheets, nanoplates, commercial BiOCl and TiO2 (anatase). The highly enhanced photocatalytic activities could be ascribed to the contributions of their hierarchical nanostructures, large BET surface areas, strong adsorption capacities and superhydrophilic properties. [Copyright &y& Elsevier]

Abstract: Monoclinic bismuth vanadate (m-BiVO4) micro-/nanostructures with different sizes and morphologies were successfully prepared via a facile and rapid microwave and ultrasonic wave combined technique. The obtained BiVO4 products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM) and UV–vis diffuse reflection spectroscopy (DRS). It was found that the solvent and pH value had a significant influence on morphology, size and crystalline structure of the product. Nut-like, potato-like and broccoli-like monoclinic BiVO4 were fabricated in different solvents. The crystal phase could be modulated by varying the pH value of reaction system. The photocatalytic activities of the products were also evaluated by the degradation of Rhodamine B (RhB) under visible light irradiation. The result revealed that the photocatalytic activities of BiVO4 nanostructures were closely related to the crystalline phase, band gap and particle size. Monoclinic BiVO4 nanoparticles with small crystal size and large band gap exhibited remarkable photocatalytic performance. [Copyright &y& Elsevier]

Abstract: Uniform sponge-like Bi2SiO5 hierarchical nanostructures were successfully prepared via a facile and template-free solvothermal method at 150°C for 6h in ethylene glycol. The product was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray microanalysis (EDX), nitrogen adsorption and UV–vis diffuse reflectance spectroscopy (DRS). The as-synthesized sponge-like Bi2SiO5 hierarchical nanostructures built up from loosely-packed thin nanoflakes possessed large BET surface area and pore volume. It also exhibited excellent Cr(VI) adsorption performance, demonstrating a promising application in wastewater treatment. The as-prepared sponge-like Bi2SiO5 hierarchical nanostructures also showed similar optical property and band gap compared with TiO2, indicating that it could be used as a potential photocatalyst. [Copyright &y& Elsevier]

Abstract: Ordered flower-like zinc oxide (ZnO) nanostructures were fabricated via a facile microwave and ultrasonic combined technique. The product was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction pattern (SAED). The flower-like ZnO nanostructures were assembled by a central petal and six symmetrical petals which grew radially from the center. The flower-like ZnO sample showed an enhanced photocatalytic performance compared with the ZnO microrods for the methylene blue (MB) degradation, which could be attributed to its special structure feature. Au/ZnO and Ag/ZnO nanocomposites were also synthesized and exhibited enhanced photocatalytic efficiency after decorating noble metal nanoparticles on the surface of flower-like ZnO nanostructures. [Copyright &y& Elsevier]

Abstract: A facile and rapid microwave irradiation method was explored for the synthesis of bismuth phosphate (BiPO4) nanostructures with various morphologies and phases in different solvents. The BiPO4 products were characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), UV–vis diffuse reflection spectroscopy (DRS). The effect of the solvents on the formation of the BiPO4 nanostructures was discussed on the basis of experimental results. The different BiPO4 nanostructures exhibited different optical properties, BET surface areas and photocatalytic activities on the degradation of methyl orange (MO) under UV and visible light irradiation. The experimental results suggested that the photocatalytic activity was closely relative with the crystalline phase and band gap of BiPO4. Hexagonal BiPO4 nanoparticles with narrow band gap showed the highest photocatalytic performance. [Copyright &y& Elsevier]

Pseudo-Z-scheme Interfacial Charge Transfer between Semiconductor and Nanocluster for Heterogeneous Photocatalysis. Ni 6 (SCH 2 Ph) 12 nanocluster as active sites of TiO 2 for heterogeneous photocatalytic hydrogen evolution via a dynamic excitation and electron-hole recombination process without strong interaction between them. [Display omitted] • Ni 6 (SCH 2 Ph) 12 is developed as cocatalyst of TiO 2 for photocatalytic H 2 evolution. • Strikingly enhanced H 2 evolution is achieved upon the Ni 6 /TiO 2 nanocomposite. • Efficient charge transfer between TiO 2 and Ni 6 is realized via non-bond interaction. • A pseudo-Z-scheme charge transfer route is proposed to illustrate the photocatalysis. Solar energy driven photocatalytic hydrogen (H 2) evolution over nanocluster modified semiconductor-based photocatalysts and understanding the charge transfer between the interface of nanocluster and semiconductor is of great importance. In this work, a benzyl thiol protected nickel nanocluster (Ni 6 (SCH 2 Ph) 12) is developed as co-catalyst for the photocatalytic hydrogen evolution over TiO 2 catalyst. By mildly depositing the nanocluster onto the TiO 2 surface, a thirty times enhancement of hydrogen evolution efficiency and an evolution rate of 5600 μmol g−1 cat h−1 is achieved under simulated sunlight irradiation. It is found that the presence of visible light could not simulate catalytic activity solely, however, it could be a promoter to improve the hydrogen evolution efficiency of Ni 6 /TiO 2 upon ultraviolet irradiation. The boosting photocatalytic hydrogen evolution is ascribed to the efficient electron transfer from TiO 2 to the nanocluster via a dynamic excitation and electron-hole recombination process assisted by the benzyl group of the ligands, which is evidenced by experimental characterizations and DFT calculations. A pseudo-Z-scheme charge transfer route under simulated solar light irradiation is proposed to illustrate the enhancement of heterogeneous photocatalysis. [ABSTRACT FROM AUTHOR]

• Bi/Bi 2 WO 6-x are fabricated by regulating the reaction time and Bi/W molar ratio. • Enhanced 1O 2 production is realized by modulating the metallic Bi and oxygen vacancy. • Bi/Bi 2 WO 6-x exhibit excellent activity for BPA and its analogues photodegradation. • The effect of solution chemistry factors and the mechanism are explored extensively. Bi/Bi 2 WO 6-x heterostructures has been successfully prepared by a facile one-step hydrothermal method. By maneuvering reaction time and Bi/W molar ratio of the precursors, we have been able to selectively introduce oxygen vacancy and metallic Bi into Bi 2 WO 6 nanostructures. The obtained Bi/Bi 2 WO 6-x heterostructures with more oxygen vacancy and moderate metallic Bi exhibit significantly improved photocatalytic activity for the photodegradation of bisphenol A (BPA) and its analogues due to its great ability for the generation of singlet oxygen (1O 2), which has proven to work as the main reactive oxygen species during photocatalysis. It is also found the 1O 2 concentration is highly depended on and modulated by the content of oxygen vacancy and metallic bismuth. Besides, we also demonstrate that the obtained Bi/Bi 2 WO 6-x products display efficient photocatalytic performance toward BPA derivatives degradation and enhanced stability to resist the interferences in the water matrix. [ABSTRACT FROM AUTHOR]