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Chinese Journal of Catalysis
2021, Vol. 42, No. 6
Online: 18 June 2021

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Cover: Shuangyin Wang’s group of Hunan University reported that nitrogen doped carbon can be electronically regulated to obtain superior oxygen reduction catalysts from the perspective of reducing surface work function. The low work function metal cesium was used to dope the carbon material, and the Cs modified nitrogen doped carbon was obtained. Read more about the article behind the cover on pages 938-944.

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Research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts Mo Zhang, Huijie Li, Junhao Zhang, Hongjin Lv, Guo-Yu Yang 2021, 42 (6):  855-871.  DOI: 10.1016/S1872-2067(20)63714-7 Abstract ( 183 )   HTML ( 99 )   PDF (4271KB) ( 718 )   With the increasing concerns to energy shortage and environmental problems in modern society, the development of cheap, clean, and sustainable energy alternatives has been attracting tremendous attention globally. Among various strategies of renewable energy exploration, solar-driven water splitting into its compositional elements H2 and O2 is an ideal approach to convert and store renewable solar energy into chemical bonds. In recent few decades, as an emerging new type of catalysts, polyoxometalates (POMs) have been widely utilized for water splitting due to their versatile synthetic methodology and highly tunable physicochemical and photochemical properties. This critical review addresses the research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts, including plenary POMs, transition-metal-substituted POMs, POM@MOF composites, and POM-semiconductor hybrids, under UV, near UV and visible light irradiation. In addition, the catalytic mechanism for each reaction system has been thoroughly discussed and summarized. Finally, a comprehensive outlook of this research area is also prospected.

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Design of metal-organic frameworks (MOFs)-based photocatalyst for solar fuel production and photo-degradation of pollutants Xiaoxue Zhao, Jinze Li, Xin Li, Pengwei Huo, Weidong Shi 2021, 42 (6):  872-903.  DOI: 10.1016/S1872-2067(20)63715-9 Abstract ( 263 )   HTML ( 21 )   PDF (4782KB) ( 749 )   Metal organic frameworks (MOFs) is a research hotspot in the solar fuel production and photo-degradation of pollutants field due to high surface area, rich metal/organic species, large pore volume, and adjustability of structures and compositions. Therefore, in this review, we first summarized the design factors of photocatalytic materials based on MOF from the perspective of "star" MOF. The modification strategies of MOFs-based photocatalysts were discussed to improve its photocatalytic activity and specific applications were summarized as well, including photocatalytic CO2 reduction, photocatalytic water splitting and photo-degradation of pollutants. Finally, the advantages and disadvantages of MOFs-based photocatalysts were discussed, the current challenges were highlighted, and suggestions for future research directions were proposed.

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Recent strategies to enhance the efficiency of hematite photoanodes in photoelectrochemical water splitting Dinghua Zhou, Ke Fan 2021, 42 (6):  904-919.  DOI: 10.1016/S1872-2067(20)63712-3 Abstract ( 186 )   HTML ( 10 )   PDF (5589KB) ( 442 )   Photoelectrochemical (PEC) water splitting is one of the most promising approaches toward achieving the conversion of solar energy to hydrogen. Hematite is a widely applied photoanode material in PEC water splitting because of its appropriate band structure, non-toxicity, high stability, and low cost. Nevertheless, its relatively low photochemical conversion efficiency limits its application, and enhancing its PEC water splitting efficiency remains a challenge. Consequently, increasing efforts have been rendered toward improving the performance of hematite photoanodes. The entire PEC water splitting efficiency typically includes three parts: the photon absorption efficiency, the separation efficiency of the semiconductor bulk, and the surface injection efficiency. This review briefly discusses the recent advances in studies on hematite photoanodes for water splitting, and through the enhancement of the three above-mentioned efficiencies, the corresponding strategies toward improving the PEC performance of hematite are comprehensively discussed and summarized.

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Progress of electrochemical CO2 reduction reactions over polyoxometalate-based materials Jing Du, Yuan-Yuan Ma, Huaqiao Tan, Zhen-Hui Kang, Yangguang Li 2021, 42 (6):  920-937.  DOI: 10.1016/S1872-2067(20)63718-4 Abstract ( 253 )   HTML ( 17 )   PDF (3964KB) ( 633 )   Electrochemical CO2 reduction to value-added fuels and chemicals is recognized as a promising strategy to alleviate energy shortages and global warming owing to its high efficiency and economic feasibility. Recently, understanding the activity origin, selectivity regulation, and reaction mechanisms of CO2 reduction reactions (CO2RRs) has become the focus of efficient electrocatalyst design. Polyoxometalates (POMs), a unique class of nanosized metal-oxo clusters, are promising candidates for the development of efficient CO2RR electrocatalysts and, owing to their well-defined structure, remarkable electron/proton storage and transfer ability, and capacities for adsorption and activation of CO2, are ideal models for investigating the activity origin and reaction mechanisms of CO2RR electrocatalysts. In this review, we focus on the activity origin and mechanism of CO2RRs and survey recent advances that were achieved by employing POMs in electrocatalytic CO2RRs. We highlight the significant roles of POMs in the electrocatalytic CO2RR process and the main factors influencing selectivity regulation and catalytic CO2RR performance, including the electrolyte, electron-transfer process, and surface characteristics. Finally, we offer a perspective of the advantages and future challenges of POM-based materials in electrocatalytic CO2 reduction that could inform new advancements in this promising research field.

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Regulating carbon work function to boost electrocatalytic activity for the oxygen reduction reaction Yazhi Cai, Li Tao, Gen Huang, Nana Zhang, Yuqin Zou, Shuangyin Wang 2021, 42 (6):  938-944.  DOI: 10.1016/S1872-2067(20)63701-9 Abstract ( 429 )   HTML ( 24 )   PDF (2286KB) ( 507 )   Supporting Information Electronic regulation of carbon is essential for developing non-platinum electrocatalysts for oxygen reduction reactions (ORRs). In this work, we used Cs to further regulate the electronic structure of nitrogen-doped (N-doped) carbon. The Cs atoms coordinated with the nitrogen atom in the N-doped carbon for injecting electrons into the carbon conjugate structure and reducing the work function of the carbon network. The low-work-function surface improved electron donation, facilitated O2 dissociation, and enhanced the adsorption of an OOH* intermediate. Thus, electrocatalytic performance for the ORR was improved. The material shows potential as an ORR electrocatalyst comparable with Pt/C.

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Intrinsic photocatalytic water oxidation activity of Mn-doped ferroelectric BiFeO3 Jafar Hussain Shah, Anum Shahid Malik, Ahmed Mahmoud Idris, Saadia Rasheed, Hongxian Han, Can Li 2021, 42 (6):  945-952.  DOI: 10.1016/S1872-2067(20)63713-5 Abstract ( 152 )   HTML ( 13 )   PDF (2300KB) ( 444 )   Supporting Information The development of stable and efficient visible light-absorbing oxide-based semiconductor photocatalysts is a desirable task for solar water splitting applications. Recently, we proposed that the low photocurrent density in film-based BiFeO3 (BFO) is due to charge recombination at the interface of the domain walls, which could be largely reduced in particulate photocatalyst systems. To demonstrate this hypothesis, in this work we synthesized particulate BFO and Mn-doped BiFeO3 (Mn-BFO) by the sol-gel method. Photocatalytic water oxidation tests showed that pure BFO had an intrinsic photocatalytic oxygen evolution reaction (OER) activity of 70 μmol h-1g-1, while BFO-2, with an optimum amount of Mn doping (0.05%), showed an OER activity of 255 μmol h -1g-1under visible light (λ ≥ 420 nm) irradiation. The bandgap of Mn-doped BFO could be reduced from 2.1 to 1.36 eV by varying the amount of Mn doping. Density functional theory (DFT) calculations suggested that surface Fe (rather than Mn) species serve as the active sites for water oxidation, because the overpotential for water oxidation on Fe species after Mn doping is 0.51 V, which is the lowest value measured for the different Fe and Mn species examined in this study. The improved photocatalytic water oxidation activity of Mn-BFO is ascribed to the synergistic effect of the bandgap narrowing, which increases the absorption of visible light, reduces the activation energy of water oxidation, and inhibits the recombination of photogenerated charges. This work demonstrates that Mn doping is an effective strategy to enhance the intrinsic photocatalytic water oxidation activity of particulate ferroelectric BFO photocatalysts.

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N-doped carbon-coated Fe3N composite as heterogeneous electro-Fenton catalyst for efficient degradation of organics Juan Xiao, Junwei Chen, Zuqiao Ou, Junhang Lai, Tongwen Yu, Yi Wang 2021, 42 (6):  953-962.  DOI: 10.1016/S1872-2067(20)63719-6 Abstract ( 163 )   HTML ( 8 )   PDF (3340KB) ( 439 )   Supporting Information Herein, the application of a N-doped graphitic-carbon-coated iron nitride composite dispersed in a N-doped carbon framework (Fe3N@NG/NC) is investigated as a heterogeneous electro-Fenton ( HE-EF) catalyst for the efficient removal of organics. The simultaneous carbonization and ammonia etching of iron-based metal organic framework (Fe-MOF) materials yielded well-dispersed N-doped carbon-coated Fe3N nanoparticles with a diameter of ~70 nm. The Fe3N and pyridinic N endowed the composite with high HE-EF activity for decomposing the electrogenerated H2O2 to•OH. The Fe3N@NG/NC exhibited outstanding HE-EF performance in removing various organic pollutants with low iron leaching. A removal rate of 97-100% could be obtained for rhodamine B (RhB), dimethyl phthalate, methylene blue, and orange II in 120 min at a pH of 5.0. When the solution pH was set to 3.0, 5.0, 7.0, and 9.0, the removal rate of RhB reached 100%, 96%, 92%, and 81%, respectively, in 60 min at an optimum voltage of 0.0 V (vs. reversible hydrogen electrode (RHE)). Moreover, the concentration of leached iron was expected to be below 0.03 mg/L in a wide pH range of 3.0-9.0. In addition, the RhB removal efficiency remained as high as 90% after six cycles in the reusability experiments. This work highlights the MOF-derived Fe3N composite as an efficient HE-EF catalyst and the corresponding catalytic mechanism, which facilitates its application in wastewater treatment.

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Enhanced oxygen reduction reaction performance over Pd catalysts by oxygen-surface-modified SiC Jing Li, Xiang Sun, Yongzheng Duan, Dongmei Jia, Yuejin Li, Jianguo Wang 2021, 42 (6):  963-970.  DOI: 10.1016/S1872-2067(20)63716-0 Abstract ( 102 )   HTML ( 6 )   PDF (1686KB) ( 410 )   Supporting Information Obtaining a detailed understanding of the surface modification of supports is crucial; however, it is a challenging task for the development and large-scale fabrication of supported electrocatalysts that can be used as alternatives to Pt-based catalysts for the oxygen reduction reaction (ORR). In this study, commercial silicon carbide (SiC) was modified through surface oxidization (O-SiC) to support the use of Pd nanoparticles (Pd NPs) as electrocatalysts for ORR. The obtained Pd/O-SiC catalysts exhibited better ORR activity, stronger durability, and higher resistance to methanol poisoning than that exhibited by commercial Pt/C. The role of the support in enhancing the ORR performance, especially the oxidization of SiC surfaces, was discussed in detail based on the experimental characterizations and density functional theory calculations. The underlying mechanism of the superior ORR performance of Pd/O-SiC catalysts was attributed to the charge transfer from SiCxOy to Pd NPs on the surfaces of SiC and the strong metal-support interactions (SMSIs) between Pd and SiCxOy. The charge transfer enhanced the ORR activity by inducing electron-rich Pd, increased the adsorption of the key intermediate OOH, and decreased the Gibbs free energy of the critical ORR step. Furthermore, SMSIs enhanced the ORR stability of the Pd/O-SiC catalyst. This study provided a facile route for designing and developing highly active Pd-based ORR electrocatalysts.

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Atomic structures and electronic properties of Cr-doped ZnO(10$\overline{1}$0) surfaces Wugen Huang, Jun Cai, Jun Hu, Junfa Zhu, Fan Yang, Xinhe Bao 2021, 42 (6):  971-979.  DOI: 10.1016/S1872-2067(20)63710-X Abstract ( 126 )   HTML ( 12 )   PDF (2689KB) ( 1053 )   An integrated approach combining scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) is used to investigate the atomic structures and electronic properties of Cr-doped ZnO(10$\overline{1}$0) surfaces. When deposited at 300 K, Cr at low surface coverage (< 0.1 ML) appeared either as isolated atoms on the surface terrace of ZnO(10$\overline{1}$0) or substituting Zn atoms in the ZnO lattice. Their structural models could be identified from atomic-resolution STM images and their oxidation states were found as Cr3+ based on XPS measurements. Rectangular islands nucleated at step edges along the [0001] direction could also be observed during the initial growth of Cr at 300 K and were assigned as Cr islands. The density of Cr islands as well as their average size increased with the increasing of Cr surface loading. Thermal treatments at above 600 K could facilitate the decomposition of Cr islands and the re-dispersion of Cr atoms into the ZnO lattice, indicating a strong interaction between Cr and ZnO. The adsorption of CO at 78 K showed no preferential adsorption at Cr3+ sites embedded in the surface lattice of ZnO. However, the re-dispersion of Cr atoms into the ZnO bulk at above 600 K could induce a significant upward band bending, causing a negative shift of core level XPS peaks of Zn 2p and O 1s by ~0.5-0.7 eV. Our study has thus constructed a model catalyst for Cr-doped ZnO and provided atomic insight for understanding ZnO-based catalysts.

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Critical roles of molybdate anions in enhancing capacitive and oxygen evolution behaviors of LDH@PANI nanohybrids Qiang Hu, Hua Wang, Feifei Xiang, Qiaoji Zheng, Xinguo Ma, Yu Huo, Fengyu Xie, Chenggang Xu, Dunmin Lin, Jisong Hu 2021, 42 (6):  980-993.  DOI: 10.1016/S1872-2067(20)63724-X Abstract ( 152 )   HTML ( 11 )   PDF (3622KB) ( 490 )   Supporting Information Low-overpotential layered hydroxides (LDHs) with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction; however, the low electronic conductivity and insufficient active sites of bulk LDHs increase the internal resistance and reduce the capacity and oxygen-production efficiency of electrodes. Herein, we prepared a polyaniline-coated NiCo-layered double hydroxide intercalated with MoO42- (M-LDH@PANI) composite electrode using a two-step method. As the amount of MoO42- in the LDH increases, acicular microspheres steadily evolve into flaky microspheres with a high surface area, providing more active electrochemical sites. Moreover, the amorphous PANI coating of M-LDH boosts the electronic conductivity of the composite electrode. Accordingly, the M-LDH@PANI at an appropriate level of MoO42- exhibits significantly enhanced energy storage and catalytic performance. Experimental analyses and theoretical calculations reveal that a small amount of MoO42- is conducive to the expansion of LDH interlayer spacing, while an excessive amount of MoO42- combines with the H atoms of LDH, thus competing with OH-, resulting in reduced electrochemical performance. Moreover, M-LDH flaky microspheres can efficiently modulate deprotonation energy, greatly accelerating surface redox reactions. This study provides an explanation for an unconventional mechanism, and a method for the modification of LDH-based materials for anion intercalation.

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Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid Xiaoling Liu, Lei Chen, Hongzhong Xu, Shi Jiang, Yu Zhou, Jun Wang 2021, 42 (6):  994-1003.  DOI: 10.1016/S1872-2067(20)63720-2 Abstract ( 117 )   HTML ( 8 )   PDF (2208KB) ( 498 )   Supporting Information Encapsulating noble metal nanoparticles (NPs) within the zeolite framework enhances the stability and accessibility of active sites; however, direct synthesis remains a challenge because of the easy precipitation of noble metal species under strong alkali crystallization conditions. Herein, beta zeolite-encapsulated Pt NPs (Pt@Beta) were synthesized via a hydrothermal approach involving an unusual acid hydrolysis preaging step. The ligand—(3-mercaptopropyl)trimethoxysilane—and Pt precursor were cohydrolyzed and cocondensed with a silica source in an initially weak acidic environment to prevent colloidal precipitation by enhancing the interaction between the Pt and silica species. Thus, the resultant 0.2%Pt@Beta was highly active in the transformation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid (FDCA) under atmospheric O2 conditions by using water as the solvent while stably evincing a high yield (90%) associated with a large turnover number of 176. The excellent catalysis behavior is attributable to the enhanced stability that inhibits Pt leaching and strengthens the intermediates that accelerate the rate-determining step for the oxidation of 5-formyl-2-furan carboxylic acid into FDCA.

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Surface assembly of cobalt species for simultaneous acceleration of interfacial charge separation and catalytic reactions on Cd0.9Zn0.1S photocatalyst Khakemin Khan, Lifen Xu, Ming Shi, Jiangshan Qu, Xiaoping Tao, Zhaochi Feng, Can Li, Rengui Li 2021, 42 (6):  1004-1012.  DOI: 10.1016/S1872-2067(20)63717-2 Abstract ( 230 )   HTML ( 18 )   PDF (2850KB) ( 425 )   Supporting Information Although photocatalytic water splitting has excellent potential for converting solar energy into chemical energy, the challenging charge separation process and sluggish surface catalytic reactions significantly limit progress in solar energy conversion using semiconductor photocatalysts. Herein, we demonstrate a feasible strategy involving the surface assembly of cobalt oxide species (CoOx) on a visible-light-responsive Cd0.9Zn0.1S (CZS) photocatalyst to fabricate a hierarchical CZS@CoOx heterostructure. The unique hierarchical structure effectively accelerates the directional transfer of photogenerated charges, reducing charge recombination through the smooth interfacial heterojunction between CZS and CoOx, as evidenced by photoluminescence (PL) spectroscopy and various electrochemical characterizations. The surface cobalt species on the CZS material also act as efficient cocatalysts for photocatalytic hydrogen production, with activity even higher than that of noble metals. The well-defined CZS@CoOx heterostructure not only enhances the interfacial separation of photoinduced charges, but also improves surface catalytic reactions. This leads to superior photocatalytic performances, with an apparent quantum efficiency of 20% at 420 nm for visible-light-driven hydrogen generation, which is one of the highest quantum efficiencies measured among noble-metal-free photocatalysts. Our work presents a potential pathway for controlling complex charge separation and catalytic reaction processes in photocatalysis, guiding the practical development of artificial photocatalysts for successful transformation of solar to chemical energy.

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Chloridion-induced dual tunable fabrication of oxygen-deficient Bi2WO6 atomic layers for deep oxidation of NO Xianglong Yang, Shengyao Wang, Ting Chen, Nan Yang, Kai Jiang, Pei Wang, Shu Li, Xing Ding, Hao Chen 2021, 42 (6):  1013-1023.  DOI: 10.1016/S1872-2067(20)63708-1 Abstract ( 79 )   HTML ( 4 )   PDF (4829KB) ( 361 )   Supporting Information Engineering an efficient interface is a trustworthy strategy for designing advanced photocatalytic systems for solar energy conversion. Herein, oxygen-deficient Bi2WO6 atomic layers without organic residues were successfully fabricated via a facile solvothermal strategy by the multifunctional regulatory mechanism of introduced chloridion. Both DFT calculations and speciation determination revealed that chloridion displayed a more pronounced effect in the controllable synthesis of oxygen-deficient Bi2WO6 atomic layers without organic residues: ultrathinning and defect-engineering. This built-in multi-cooperative interface endowed Bi2WO6 with intriguing photoelectrochemical properties, O2 activation ability, and ultrahigh activity in visible-light powered deep oxidation of NO. A reasonable photocatalytic mechanism was proposed based on in situ infrared spectroscopy analysis and theoretical calculations. We believe that this multi-cooperative interface engineering of oxygen-deficient Bi2WO6 atomic layers without organic residues could provide new insights into the design of two-dimensional (2D) layered materials with efficient active sites and pave the way for efficient NO photooxidation systems.

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Commercial indium-tin oxide glass: A catalyst electrode for efficient N2 reduction at ambient conditions Ting Wang, Shaoxiong Li, Bingling He, Xiaojuan Zhu, Yonglan Luo, Qian Liu, Tingshuai Li, Siyu Lu, Chen Ye, Abdullah M. Asiri, Xuping Sun 2021, 42 (6):  1024-1029.  DOI: 10.1016/S1872-2067(20)63704-4 Abstract ( 122 )   HTML ( 8 )   PDF (2549KB) ( 519 )   Supporting Information The typical Haber technical process for industrial NH3 production involves plenty of energy-consumption and large quantities of greenhouse gas emission. In contrast, electrochemical N2 reduction proffers environment-friendly and energy-efficient avenues to synthesize NH3 at mild conditions but demands efficient electrocatalysts for the N2 reduction reaction (NRR). Herein we report for the first time that commercial indium-tin oxide glass (ITO/G) can be used as a catalyst electrode toward artificial N2 fixation, as it demonstrates excellent selectivity at mild conditions. Such ITO/G delivers excellent NRR performance with a NH3 yield of 1.06 × 10-10 mol s-1 cm-2 and a faradaic efficiency of 6.17% at -0.40 V versus the reversible hydrogen electrode (RHE) in 0.5 M LiClO4. Furthermore, the ITO/G also possesses good electrochemical stability and durability. Finally, the possible reaction mechanism for the NRR on the ITO catalysts was explored using first-principles calculations.

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Mn-corrolazine-based 2D-nanocatalytic material with single Mn atoms for catalytic oxidation of alkane to alcohol Chun Zhu, Jin-Xia Liang, Yang Meng, Jian Lin, Zexing Cao 2021, 42 (6):  1030-1039.  DOI: 10.1016/S1872-2067(20)63707-X Abstract ( 111 )   HTML ( 9 )   PDF (2670KB) ( 403 )   Supporting Information Heterogenization of organic-macrocyclic metal catalysts is one of the simplest and most efficient methods for effective separation of products and cyclic application of a catalyst. By using an environmentally friendly Mn-corrolazine catalyst as the building unit, which can directly oxidize organic substrates under oxygen atmosphere and mild conditions, we theoretically constructed a novel two-dimensional (2D) Mn-corrolazine nanocatalytic material with high catalytic activity. In this material, each Mn atom maintains its electronic configuration in the monomer and can directly activate O2 as the single-atom catalyst (SAC) center to form a radical-like [Mn]-O-O under mild visible-light irradiation conditions. The newly generated [Mn]-O-O can efficiently and selectively oxidize C-H bonds to form alcohol species through H-abstraction and the rebound reaction. Moreover, the catalytic reaction is easily regulated by an external electric field along its intrinsic Mn-O-O reaction axis. The current study provides a theoretical foundation for further experimental studies and practical applications of the Mn-corrolazine-based SAC.

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Rational design of stratified material with spatially separated catalytic sites as an efficient overall water-splitting photocatalyst Yi-Lei Li, Xiao-Jing Wang, Ying-Juan Hao, Jun Zhao, Ying Liu, Hui-Ying Mu, Fa-Tang Li 2021, 42 (6):  1040-1050.  DOI: 10.1016/S1872-2067(20)63706-8 Abstract ( 117 )   HTML ( 6 )   PDF (3090KB) ( 424 )   Supporting Information The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active sites. Moreover, in the process of water oxidation catalysis, the inhibition of severe photocorrosion is an immense task, requiring effective photogenic hole-transfer kinetics. Herein, stratified Co-MnO2@CdS/CoS hollow cubes with spatially separated catalytic sites were rationally designed and fabricated as highly efficient controllable catalysts for photocatalytic overall water splitting. The unique self-templated method, including a continuous anion/cation-exchange reaction, integrates a Co-doped oxidation co-catalyst (Co-MnO2) and a reduction co-catalyst (CoS) on the nanocubes with uniform interface contact and ultrathin two-dimensional (2D) nanometer sheets. We demonstrate that the stratified Co-MnO2@CdS/CoS hollow cubes can provide an abundance of active sites for surface redox reactions and contribute to the separation and migration of the photoionization charge carriers. In particular, CoS nanoparticles dispersed on the walls of CdS hollow cubes were identified as reduction co-catalysts accelerating hydrogen generation, while Co-MnO2 nanosheets attached to the inner walls of the CdS hollow cube were oxidation co-catalysts, promoting oxygen evolution dynamics. Benefiting from the desirable structural and compositional advantages, optimized stratification of Co-MnO2@CdS/CoS nanocubes provided a catalytic system devoid of precious metals, which exhibited a remarkable overall photocatalytic water-splitting rate (735.4 (H2) and 361.1 (O2) μmol h-1 g-1), being among the highest values reported thus far for CdS-based catalysts. Moreover, an apparent quantum efficiency (AQE) of 1.32% was achieved for hydrogen evolution at 420 nm. This study emphasizes the importance of rational design on the structure and composition of photocatalysts for overall water splitting.