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    Chinese Journal of Catalysis
    2022, Vol. 43, No. 4
    Online: 18 April 2022

    Cover: Sun and coworkers in their article on pages 1049–1057 reported a two-dimensional (2D) Cu-based metal organic framework (Cu MOF) modified with CuO nanoparticles for efficient electrocatalytic CO2 reduction to C2H4. The Faradaic efficiency (FE) for C2H4 formation reached up to 50.0% at -1.1 V (vs. reversible hydrogen electrode) in CO2-saturated 0.1 mol/L KHCO3 solution using an H-type cell. The FE remained over 45.0% after 10 h of continuous electrolysis. Further study showed that combination of 2D Cu MOF and ultrafine CuO nanoparticles synergistically facilitated adsorption and activation of CO2, boosting C-C coupling, thereby resulting in high C2H4 selectivity.
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    Artificial photosynthetic starch from liquid sunshine
    Wangyin Wang
    2022, 43 (4):  895-897.  DOI: 10.1016/S1872-2067(21)64023-8
    Abstract ( 223 )   HTML ( 356 )   PDF (825KB) ( 307 )  
    Account
    Rational design and precise manipulation of nano-catalysts
    Qinggang Liu, Junguo Ma, Chen Chen
    2022, 43 (4):  898-912.  DOI: 10.1016/S1872-2067(21)63933-5
    Abstract ( 491 )   HTML ( 140 )   PDF (4959KB) ( 457 )  

    Nano-catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry. The rapid technological enhancements have resulted in serious energy and environmental issues, which are currently spurring the exploration of the novel nano-catalysts in diverse fields. In order to develop the efficient nano-catalysts, it is essential to understand their fundamental physicochemical properties, including the coordination structures of the active centers and substrate-adsorbate interactions. Subsequently, the nano-catalyst design with precise manipulation at the atomic level can be attained. In this account, we have summarized our extensive investigation of the factors impacting nano-catalysis, along with the synthetic strategies developed to prepare the nano-catalysts for applications in electrocatalysis, photocatalysis and thermocatalysis. Finally, a brief conclusion and future research directions on nano-catalysis have also been presented.

    Theoretical perspective on mononuclear copper-oxygen mediated C-H and O-H activations: A comparison between biological and synthetic systems
    Peng Wu, Jinyan Zhang, Qianqian Chen, Wei Peng, Binju Wang
    2022, 43 (4):  913-927.  DOI: 10.1016/S1872-2067(21)63974-8
    Abstract ( 173 )   HTML ( 22 )   PDF (2386KB) ( 194 )  

    Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O2 activation, copper-dependent metalloenzymes such as particulate methane monooxygenases (pMMOs), lytic polysaccharide monooxygenases (LPMOs) and binuclear copper enzymes PHM and DβM, are able to perform various challenging C-H bond activations. Meanwhile, various copper-oxygen core containing complexes have been synthetized to mimic the active species of metalloenzymes. Dioxygen activation by mononuclear copper active site may generate various copper-oxygen intermediates, including Cu(II)-superoxo, Cu(II)-hydroperoxo, Cu(II)-oxyl as well as the Cu(III)-hydroxide species. Intriguingly, all these species have been invoked as the potential active intermediates for C-H/O-H activations in either biological or synthetic systems. Due to the poor understanding on reactivities of copper-oxygen complex, the nature of active species in both biological and synthetic systems are highly controversial. In this account, we will compare the reactivities of various mononuclear copper-oxygen species between biological systems and the synthetic systems. The present study is expected to provide the consistent understanding on reactivities of various copper-oxygen active species in both biological and synthetic systems.

    Reviews
    Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts
    Chunpeng Wang, Zhe Wang, Shanjun Mao, Zhirong Chen, Yong Wang
    2022, 43 (4):  928-955.  DOI: 10.1016/S1872-2067(21)63924-4
    Abstract ( 467 )   HTML ( 121 )   PDF (13513KB) ( 537 )  

    The structural complexity of supported metal catalysts, playing significant role in a wide range of chemical technologies, have prevented us from deeply understanding their catalytic mechanisms at atomic level. A fundamental understanding of the nature of active sites and structure-performance relationship of supported metal catalysts from a comprehensive view will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy conversion and environmental protection. This review surveys the effects of multiple factors, including the metal size, shape, support, alloy and ligand modifier, on the coordinated environment of active center and further their influence on the catalytic reactions, aiming to provide guidance for the design of industrialized heterogeneous catalysts with extraordinary performance. Subsequently, the key structure characterization techniques in determining the coordination structure of active metal sites, especially the dynamic coordination structure change under the reaction condition, are well summarized. A brief summary is finally provided together with personal perspectives on the further development in the field of heterogeneous metal catalysts.

    Photo- and electro-catalytic deuteration of feedstock chemicals and pharmaceuticals: A review
    Wei Ou, Chuntian Qiu, Chenliang Su
    2022, 43 (4):  956-970.  DOI: 10.1016/S1872-2067(21)63928-1
    Abstract ( 456 )   HTML ( 22 )   PDF (2785KB) ( 435 )  

    Deuterium labeling techniques are widely utilized as efficient tools to study the absorption, distribution, metabolism, and excretion (ADME) of pharmaceuticals. Moreover, deuterium-labeled drugs are expected to prolong the half-life of drug metabolism, enhance the efficacy of drugs, close metabolic sites, and decrease side effects. Thus, there is a rising demand for the practical construction of deuterium-labeled drugs and their intermediates under mild conditions. This paper timely provides an overview of the recent advances in both photo- and electro-catalytic mild and selective deuteration of fine chemicals and pharmaceuticals with low-cost and sustainable deuterium source. Three types of deuteration strategies are discussed according to the deuteration mode, named deuterium atom transfer strategy, deuterium atom abstraction strategy and deuterated water splitting strategy respectively. The application scope and mechanistic insights are discussed comprehensively. Finally, the perspective on the challenges and future development trends for photo- and electro-catalytic deuteration strategies are also presented.

    Metal-organic framework-derived multifunctional photocatalysts
    Yaping Zhang, Jixiang Xu, Jie Zhou, Lei Wang
    2022, 43 (4):  971-1000.  DOI: 10.1016/S1872-2067(21)63934-7
    Abstract ( 356 )   HTML ( 27 )   PDF (18744KB) ( 750 )  

    Metal-organic framework (MOF)-derived nanomaterials have attracted widespread attention, because the excellent features, such as high surface area, porosity and tunable properties are inherited from MOFs. Moreover, the derivatives avoid the poor conductivity and stability of MOFs. MOF-derived nanomaterials can easily be regulated by a specific selection of metal nodes and organic linkers, resulting in multifunctionality in photocatalysis. MOF derivatives can be used not only as semiconductor photocatalysts, but also as co-catalysts for photocatalytic hydrogen evolution, CO2 reduction, pollutants degradation, etc. This review focuses on the multifunctional applications of MOF derivatives in the field of photocatalysis. The researches in recent years are analyzed and summarized from the aspects of preparation, modification and application of MOF derivatives. At the end of the review, the development and challenges of MOF derivatives applied in photocatalysis in the future are put forward, in order to provide more references for further research in this field and bring new inspiration.

    Electrochemical synthesis of catalytic materials for energy catalysis
    Dunfeng Gao, Hefei Li, Pengfei Wei, Yi Wang, Guoxiong Wang, Xinhe Bao
    2022, 43 (4):  1001-1016.  DOI: 10.1016/S1872-2067(21)63940-2
    Abstract ( 614 )   HTML ( 42 )   PDF (3387KB) ( 332 )  

    Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy. Precise synthesis of catalytically active nanostructures is one of the key challenges that hinder the practical application of many important energy-related electrocatalytic reactions. Compared with conventional wet-chemical, solid-state and vapor deposition synthesis, electrochemical synthesis is a simple, fast, cost-effective and precisely controllable method for the preparation of highly efficient catalytic materials. In this review, we summarize recent progress in the electrochemical synthesis of catalytic materials such as single atoms, spherical and shaped nanoparticles, nanosheets, nanowires, core-shell nanostructures, layered nanomaterials, dendritic nanostructures, hierarchically porous nanostructures as well as composite nanostructures. Fundamental aspects of electrochemical synthesis and several main electrochemical synthesis methods are discussed. Structure-performance correlations between electrochemically synthesized catalysts and their unique electrocatalytic properties are exemplified using selected examples. We offer the reader with a basic guide to the synthesis of highly efficient catalysts using electrochemical methods, and we propose some research challenges and future opportunities in this field.

    Design strategies and structure-performance relationships of heterogeneous catalysts for selective hydrogenation of 1,3-butadiene
    Mengru Wang, Yi Wang, Xiaoling Mou, Ronghe Lin, Yunjie Ding
    2022, 43 (4):  1017-1041.  DOI: 10.1016/S1872-2067(21)63942-6
    Abstract ( 314 )   HTML ( 16 )   PDF (6317KB) ( 306 )  

    Selective hydrogenation of 1,3-butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector. Catalyst design is crucial to achieve a virtually alkadiene-free product while avoiding over-hydrogenating valuable olefins. In addition to the great industrial relevance, this demanding selectivity pattern renders 1,3-butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia. Nonetheless, critical reviews on the catalyst development are extremely lacking in literature. In this review, we aim to provide the reader an in-depth overview of different catalyst families, particularly the precious metal-based monometallic catalysts (Pd, Pt, and Au), developed in the last half century. The emphasis is placed on the development of new strategies to design high-performance architectures, the establishment of structure-performance relationships, and the reaction and deactivation mechanisms. Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.

    Communication
    Precise and controllable tandem strategy triggering boosted oxygen reduction activity
    Guoxing Jiang, Longhai Zhang, Wenwu Zou, Weifeng Zhang, Xiujun Wang, Huiyu Song, Zhiming Cui, Li Du*
    2022, 43 (4):  1042-1048.  DOI: 10.1016/S1872-2067(21)63966-9
    Abstract ( 171 )   HTML ( 11 )   PDF (2918KB) ( 287 )  
    Supporting Information

    The development of efficient and cost-effective metal-free electrocatalysts for oxygen reduction reaction (ORR) has become crucial for electrochemical energy systems. However, reasonably validating and precisely regulating the active sites for designing optimized materials are still challenging. Herein, we report a precise and controllable tandem strategy to boost the ORR activity based on metal-free covalent organic frameworks (MFCOFs) comprising imine-N, thiophene-S, or triazine-N. Among these MFCOFs, post-tandem BTT-TAT-COF structure displayed a more positive catalytic capability and excellent electrochemical stability, indicating that the synergistic catalysis of multiple active sites induced the ORR catalytic activity through the conjugated skeleton of the structure. Density-functional theory calculations suggest that the series-connected backbone contained highly effective electrocatalytic active centers and provided synergistic catalysis. More importantly, this strategy highlights new opportunities for the advancement of efficient COF-based metal-free ORR catalysts.

    Articles
    Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO2 reduction to ethylene
    Linlin Wang, Xin Li, Leiduan Hao, Song Hong, Alex W. Robertson, Zhenyu Sun
    2022, 43 (4):  1049-1057.  DOI: 10.1016/S1872-2067(21)63947-5
    Abstract ( 345 )   HTML ( 20 )   PDF (4250KB) ( 472 )  
    Supporting Information

    To facilitate the electrochemical CO2 reduction (ECR) to fuels and valuable chemicals, the development of active, low cost, and selective catalysts is crucial. We report a novel ECR catalyst consisting of CuO nanoparticles with sizes ranging from 1.4 to 3.3 nm anchored on Cu metal-organic framework (Cu-MOF) nanosheets obtained through a one-step facile solvothermal method. The nanocomposites provide multiple sites for efficient ambient ECR, delivering an average C2H4 faradaic efficiency (FE) of ~50.0% at -1.1 V (referred to the reversible hydrogen electrode) in 0.1 mol/L aqueous KHCO3 using a two-compartment cell, in stark contrast to a C2H4 FE of 25.5% and 37.6% over individual CuO and Cu-MOF respectively, also surpassing most newly reported Cu-based materials under similar cathodic voltages. The C2H4 FE remains at over 45.0% even after 10.0 h of successive polarization. Also, a ~7.0 mA cm-2C2H4 partial geometric current density and 27.7% half-cell C2H4 power conversion efficiency are achieved. The good electrocatalytic performance can be attributed to the interface between CuO and Cu-MOF, with accessible metallic moieties and the unique two-dimensional structure of the Cu-MOF enhancing the adsorption and activation of CO2 molecules. This finding offers a simple avenue to upgrading CO2 to value-added hydrocarbons by rational design of MOF-based composites.

    Rapid synthesis of Pd single-atom/cluster as highly active catalysts for Suzuki coupling reactions
    Hehe Wei, Xiaoyang Li, Bohan Deng, Jialiang Lang, Ya Huang, Xingyu Hua, Yida Qiao, Binghui Ge, Jun Ge, Hui Wu
    2022, 43 (4):  1058-1065.  DOI: 10.1016/S1872-2067(21)63968-2
    Abstract ( 193 )   HTML ( 7 )   PDF (2282KB) ( 199 )  
    Supporting Information

    Palladium (Pd)-based catalysts are essential to drive high-performance Suzuki coupling reactions, which are powerful tools for the synthesis of functional organic compounds. Herein, we developed a solution-rapid-annealing process to stabilize nitrogen-mesoporous carbon supported Pd single-atom/cluster (Pd/NMC) material, which provided a catalyst with superior performance for Suzuki coupling reactions. In comparison with commercial palladium/carbon (Pd/C) catalysts, the Pd/NMC catalyst exhibited significantly boosted activity (100% selectivity and 95% yield) and excellent stability (almost no decay in activity after 10 reuse cycles) for the Suzuki coupling reactions of chlorobenzenes, together with superior yield and excellent selectivity in the fields of the board scope of the reactants. Moreover, our newly developed rapid annealing process of precursor solutions is applied as a generalized method to stabilize metal clusters (e.g. Pd, Pt, Ru), opening new possibilities in the construction of efficient highly dispersed metal atom and sub-nanometer cluster catalysts with high performance.

    Crystal facet effect induced by different pretreatment of Cu2O nanowire electrode for enhanced electrochemical CO2 reduction to C2+ products
    Yang Fu, Qixian Xie, Linxiao Wu, Jingshan Luo
    2022, 43 (4):  1066-1073.  DOI: 10.1016/S1872-2067(21)63981-5
    Abstract ( 317 )   HTML ( 23 )   PDF (3351KB) ( 497 )  
    Supporting Information

    Electrocatalytic CO2 conversion has been considered as a promising way to recycle CO2 and produce sustainable fuels and chemicals. However, the efficient and highly selective electrochemical reduction of CO2 directly into multi-carbon (C2+) products remains a great challenge. Herein, we synthesized three type catalysts with different morphologies based on Cu2O nanowires, and studied their morphology and crystal facet reconstruction during the pre-reduction process. Benefiting from abundant exposure of Cu (100) crystal facet, the nanosheet structure derived Cu catalyst showed a high faradaic efficiency (FE) of 67.5% for C2+ products. Additionally, electrocatalytic CO2 reduction studies were carried out on Cu(100), Cu(110), and Cu(111) single crystal electrodes, which verified that Cu(100) crystal facets are favorable for the C2+ products in electrocatalytic CO2 reduction. Our work showed that catalysts would reconstruct during the CO2 reduction process and the importance in morphology and crystal facet control to obtain desired products.

    Novel core-shell Ag@AgSex nanoparticle co-catalyst: In situ surface selenization for efficient photocatalytic H2 production of TiO2
    Wei Zhong, Jiachao Xu, Ping Wang, Bicheng Zhu, Jiajie Fan, Huogen Yu
    2022, 43 (4):  1074-1083.  DOI: 10.1016/S1872-2067(21)63969-4
    Abstract ( 103 )   HTML ( 5 )   PDF (2774KB) ( 252 )  
    Supporting Information

    Effective charge separation and rapid interfacial H2 production are imperative for the construction of efficient photocatalysts. Compared to Pt, the metallic Ag co-catalyst with its strong electron-trapping ability and excellent electronic conductivity typically exhibits an extremely limited photocatalytic H2-evolution rate owing to its sluggish interfacial H2-generation reaction. In this study, amorphous AgSex was incorporated in situ onto metallic Ag as a novel and excellent H2-evolution active site to boost the interfacial H2-generation rate of Ag nanoparticles in a TiO2/Ag system. Core-shell Ag@AgSex nanoparticle-modified TiO2 photocatalysts were prepared via a two-step pathway involving the photodeposition of metallic Ag and the selective surface selenization of metallic Ag to yield amorphous AgSex shells. The as-prepared TiO2/Ag@AgSex (20 μL) photocatalyst exhibited an excellent H2-production performance of 853.0 μmol h-1g-1, prominently outperforming the TiO2 and TiO2/Ag samples by factors of 11.6 and 2.4, respectively. Experimental investigations and DFT calculations revealed that the enhanced H2-generation activity of the TiO2/Ag@AgSex photocatalyst could be accounted by synergistic interactions of the Ag@AgSex co-catalyst. Essentially, the metallic Ag core could quickly capture and transport the photoinduced electrons from TiO2 to the amorphous AgSex shell, whereas the amorphous AgSex shell provided large active sites for boosting the interfacial H2 evolution. This study offers a facile route for the construction of novel core-shell co-catalysts for sustainable H2 evolution.

    Efficient splitting of alcohols into hydrogen and C-C coupled products over ultrathin Ni-doped ZnIn2S4 nanosheet photocatalyst
    Jing-Yu Li, Ming-Yu Qi, Yi-Jun Xu
    2022, 43 (4):  1084-1091.  DOI: 10.1016/S1872-2067(21)63931-1
    Abstract ( 174 )   HTML ( 6 )   PDF (2417KB) ( 195 )  
    Supporting Information

    Integrating selective organic synthesis with hydrogen (H2) evolution in one photocatalytic redox reaction system sheds light on the underlying approach for concurrent employment of photogenerated electrons and holes towards efficient production of solar fuels and chemicals. In this work, a facile one-pot oil bath method has been proposed to fabricate a noble metal-free ultrathin Ni-doped ZnIn2S4 (ZIS/Ni) composite nanosheet for effective solar-driven selective dehydrocoupling of benzyl alcohol into value-added C-C coupled hydrobenzoin and H2 fuel, which exhibits higher performance than pure ZIS nanosheet. The remarkably improved photoredox activity of ZIS/Ni is mainly attributed to the optimized electron structure featuring narrower band gap and suitable energy band position, which facilitates the ability of light harvesting and photoexcited charge carrier separation and transfer. Furthermore, it has been demonstrated that it is feasible to employ ZIS/Ni for various aromatic alcohols dehydrocoupling to the corresponding C-C coupled products. It is expected that this work can stimulate further interest on the establishment of innovative photocatalytic redox platform coupling clean solar fuels synthesis and selective organic conversion in a sustainable manner.

    Defect-rich BN-supported Cu with superior dispersion for ethanol conversion to aldehyde and hydrogen
    Shi-Qun Cheng, Xue-Fei Weng, Qing-Nan Wang, Bai-Chuan Zhou, Wen-Cui Li, Ming-Run Li, Lei He, Dong-Qi Wang, An-Hui Lu
    2022, 43 (4):  1092-1100.  DOI: 10.1016/S1872-2067(21)63891-3
    Abstract ( 167 )   HTML ( 11 )   PDF (4029KB) ( 258 )  
    Supporting Information

    Copper-based heterogeneous catalysts commonly exhibit uncontrolled growth of copper species under reaction conditions because of the low Hüttig temperature (surface mobility of atoms) and Tamman temperature (bulk mobility) for copper at just 134 and 405 °C, respectively. Herein, we report the use of defect-enriched hexagonal boron nitride nanosheets (BNSs) as a support to anchor the Cu species, which resulted in superior dispersion of the Cu species. The obtained Cu/BNS catalyst was highly stable for ethanol dehydrogenation, with a high selectivity of 98% for producing acetaldehyde and an exceptionally high acetaldehyde productivity of 7.33 gAcH gcat‒1h‒1under a weight hourly space velocity of 9.6 gEtOH gcat‒1h‒1. The overall performance of our designed catalyst far exceeded that of most reported heterogeneous catalysts in terms of the stability of the Cu species and the yield of acetaldehyde in this reaction. The hydroxyl groups at the defect edges of BNS were responsible for the stabilization of the copper species, and the metal-support interaction was reinforced through charge transfer, as evidenced by coupling atomic resolution images with probe molecule infrared spectroscopy and X-ray photoelectron spectroscopy. A designed in situ diffuse reflectance infrared Fourier transform spectroscopy study of ethanol/acetaldehyde adsorption further revealed that Cu/BNS favored ethanol adsorption while suppressing acetaldehyde adsorption and further side reactions. This study demonstrates a new method for designing highly dispersed Cu-based catalysts with high durability.

    Electrochemically formed PtFeNi alloy nanoparticles on defective NiFe LDHs with charge transfer for efficient water splitting
    Gen Huang, Yingying Li, Ru Chen, Zhaohui Xiao, Shiqian Du, Yucheng Huang, Chao Xie, Chungli Dong, Haibo Yi, Shuangyin Wang
    2022, 43 (4):  1101-1110.  DOI: 10.1016/S1872-2067(21)63926-8
    Abstract ( 185 )   HTML ( 9 )   PDF (3978KB) ( 309 )  
    Supporting Information

    Efficient and stable bifunctional electrocatalysts for water splitting is essential for producing hydrogen and alleviating huge energy consumption. Meanwhile, charge transfer engineering is an efficient approach to modulate the localized electronic properties of catalysts and tune the electrocatalytic performance. Herein, we tactfully fabricate PtFeNi alloys/NiFe layered double hydroxides (LDHs) heterostructure by an easily electrochemical way with a small amount of Pt. The experimental and theoretical results unravel that the charge transfer on the alloy clusters modulated by the defective substrates (NiFe LDHs), which synergistically optimizes the adsorption energy of the reaction intermediates. The electrocatalyst exhibits an ultra-low overpotential of 81 and 243 mV at the current density of 100 mA cm-2for hydrogen evolution and oxygen evolution, respectively. Furthermore, the overall water splitting indicates that PtFeNi alloys/NiFe LDHs presents an ultra-low overpotential of 265 and 406 mV to reach the current density of 10 and 300 mA cm-2, respectively. It proves that the PtFeNi alloys/NiFe LDHs catalyst is an excellent dual-function electrocatalyst for water splitting and promising for industrialization. This work provides a new electrochemical approach to construct the alloy heterostructure. The prepared heterostructures act as an ideal platform to investigate the charge re-distribution behavior and to improve the electrocatalytic activity.

    Hydrochloric acid-mediated synthesis of ZnFe2O4 small particle decorated one-dimensional Perylene Diimide S-scheme heterojunction with excellent photocatalytic ability
    Yangrui Xu, Xiaodie Zhu, Huan Yan, Panpan Wang, Minshan Song, Changchang Ma, Ziran Chen, Jinyu Chu, Xinlin Liu, Ziyang Lu
    2022, 43 (4):  1111-1122.  DOI: 10.1016/S1872-2067(21)63930-X
    Abstract ( 119 )   HTML ( 7 )   PDF (3875KB) ( 168 )  
    Supporting Information

    The recyclable and stable ZnFe2O4 small particle decorated one-dimensional perylene diimide (PDI) S-scheme heterojunction (1D PDI/ZnFe2O4) is prepared by the hydrochloric acid-mediated (HCl-mediated) strategy, interestingly, the morphology of the 1D PDI/ZnFe2O4 can also be effectively regulated by HCl-mediated process, the existence of HCl can regulate PDI into a uniform rod structure, while the co-existence of HCl and PDI can limit ZnFe2O4 to become the uniform small particles. More importantly, based on the 1D rod structure of PDI and the small size effect of ZnFe2O4, carriers can migrate to the surface more easily, which can improve the photocatalytic activity. Meanwhile, due to the appropriate energy level structure, the S-scheme heterojunction structure is formed between PDI and ZnFe2O4, which eliminates meaningless photo-generated charge carriers through recombination and introduces strong redox to further enhance the photodegradation effect, thereby, 1D PDI/ZnFe2O4 exhibits excellent photocatalytic ability, under the visible light irradiation, the degradation rate of tetracycline (TC) with 1D PDI/ZnFe2O4 (66.67%) is 9.18 times that with PDI (7.26%) and 9.73 times that with ZnFe2O4 (6.85%). This work proposes new ideas for the assembly of magnetic organic-inorganic S-scheme heterojunction photocatalysts.

    Black phosphorus incorporated cobalt oxide: Biomimetic channels for electrocatalytic water oxidation
    Xueqing Gao, Xiaomeng Liu, Shujiao Yang, Wei Zhang, Haiping Lin, Rui Cao
    2022, 43 (4):  1123-1130.  DOI: 10.1016/S1872-2067(21)63937-2
    Abstract ( 103 )   HTML ( 9 )   PDF (2800KB) ( 191 )  
    Supporting Information

    Learning from nature photosynthesis, the development of efficient artificial catalysts for water oxidation is an ongoing challenge. Herein, a lamellar cobalt oxide (CoO), black phosphorus (BP) and reduced graphene oxide (RGO) hybrid electrocatalyst is reported. BP domains are anchored on RGO and coated with CoO via P-O bonds. The widespread P-O bond network constitutes the proton acceptor and forms a proton exit channel, akin to the use of Asp61 in Photosystem II (PSII). The innermost kernel layer RGO serves as the current collector and forms an electron exit channel, mimicking the function of Tyr161 for charge transfer. The outermost encapsulation CoO layer acts as water oxidation catalyst (WOC). These biology-inspired features endow an outstanding OER performance of the hybrid material with a low overpotential of 206 mV at a current density of 10 mA cm-2. This work provides a new design guide for OER electrocatalysts through constructing two specialized channels for proton and electron transfer.

    Cobalt-regulation-induced dual active sites in Ni2P for hydrazine electrooxidation
    Bo Zhou, Mengyu Li, Yingying Li, Yanbo Liu, Yuxuan Lu, Wei Li, Yujie Wu, Jia Huo, Yanyong Wang, Li Tao, Shuangyin Wang
    2022, 43 (4):  1131-1138.  DOI: 10.1016/S1872-2067(21)63951-7
    Abstract ( 167 )   HTML ( 14 )   PDF (1950KB) ( 276 )  
    Supporting Information

    Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable. Herein, the dehydrogenation kinetics of hydrazine electrooxidation at Ni2P is adjusted by Co as the (Ni0.6Co0.4)2P catalyzes HzOR effectively with onset potential of -45 mV and only 113 mV is needed to drive the current density of 50 mA cm‒2, showing over 60 mV lower than Ni2P and Co2P. It also delivers the maximum power density of 263.0 mW cm‒2for direct hydrazine fuel cell. Detailed experimental results revealed that Co doping not only decreases the adsorption energy of N2H4 on Ni sites, lowering the energy barrier for dehydrogenation, but also acts as the active sites in the optimal reaction coordination to boost the reaction kinetics. This work represents a breakthrough in improving the catalytic performance of non-precious metal electrocatalysts for hydrazine electrooxidation and highlights an energy-saving electrochemical hydrogen production method.

    Synergistic interaction of Nb atoms anchored on g-C3N4 and H+promoting high-efficiency nitrogen reduction reaction
    Shaokang Yang, Chaonan Zhang, Dewei Rao, Xiaohong Yan
    2022, 43 (4):  1139-1147.  DOI: 10.1016/S1872-2067(21)63950-5
    Abstract ( 130 )   HTML ( 8 )   PDF (2544KB) ( 420 )  
    Supporting Information

    Nowadays catalytic nitrogen reduction reaction (NRR) by electrochemistry has attracted much attention because of its key role in producing the basic chemical product ammonia with low energy consumption. A stable and environmentally-friendly single- or multi-atom catalyst with good performance in activity and selectivity is highly desired for NRR. From density functional theory calculations, the NRR mechanisms catalyzed by Nb monomer, dimer, trimer and tetramer anchored on graphitic carbon nitride (Nbx@g-C3N4, x = 1, 2, 3, 4) have been deeply explored. It has been found that Nb3@g-C3N4 exhibits the best catalytic ability among the four catalysts with the introduction of H+. A more stable intermediate (*NH2+*H) can be found to reduce the huge free energy barrier of forming *NH3 from *NH2 directly in a multi-atom system. By analyzing the density of states and projected crystal orbital Hamilton population, a synergistic effect among Nb atoms and the adsorbed H+is responsible for reducing the overpotential of NRR. Furthermore, the competitive hydrogen evolution reaction is suppressed effectively. This work introduces a new insight in the reaction pathway in multi-atoms for developing high-efficiency NRR catalysts.

    Scalable synthesis of ultra-small Ru2P@Ru/CNT for efficient seawater splitting
    Dan Zhang, Hongfu Miao, Xueke Wu, Zuochao Wang, Huan Zhao, Yue Shi, Xilei Chen, Zhenyu Xiao, Jianping Lai, Lei Wang
    2022, 43 (4):  1148-1155.  DOI: 10.1016/S1872-2067(21)64012-3
    Abstract ( 120 )   HTML ( 11 )   PDF (3065KB) ( 213 )  
    Supporting Information

    In this study, an ultra-fast and simple solvent-free microwave method was successfully demonstrated using a series of ultra-small (~2.5 nm) surfactant-free Ru2P@Ru/CNT heterostructures for the first time. The structure has a high-density Ru component and Ru2P component interface, which accelerates the hydrogen evolution reaction (HER). The prepared Ru2P@Ru/CNT demonstrated excellent catalytic effects for the HER in alkaline media and real seawater. The experimental results indicate that ratio-optimized Ru2P@Ru/CNT (Ru2P:Ru = 66:34) requires only 23 and 29 mV to reach 10 mA cm-2in 1.0 mol/L KOH and real seawater, respectively. These values are 10 and 24 mV lower than those of commercial Pt/C in 1.0 mol/L KOH (33 mV) and real seawater (53 mV), respectively, making it among the best non-Pt HER reported in the literature. Additionally, the TOF of Ru2P@Ru/CNT in alkaline freshwater and seawater were 13.1 and 8.5 s-1, respectively. These exceed the corresponding values for Pt/C, indicating that the catalyst has excellent intrinsic activity. The high current activity of Ru2P@Ru/CNT in 1.0 mol/L KOH was explored, and only 77 and 104 mV were required to reach 500 and 1000 mA cm-2, respectively. After 100 h of durability testing, the catalyst retained excellent catalytic and structural stability in low current density, high current density, and seawater.

    Toluene methylation with syngas to para-xylene by bifunctional ZnZrOx-HZSM-5 catalysts
    Xiaoqin Han, Jiachang Zuo, Danlu Wen, Youzhu Yuan
    2022, 43 (4):  1156-1164.  DOI: 10.1016/S1872-2067(21)63975-X
    Abstract ( 192 )   HTML ( 8 )   PDF (1322KB) ( 204 )  
    Supporting Information

    Toluene methylation with methanol on H-ZSM-5 (Z5) zeolite for the directional transformation of toluene to xylene has been industrialized. However, great challenges remain because of the high energy barrier of methanol deprotonation to the methoxy group, the side reaction of methanol to olefins, coke formation, and the deactivation of zeolites. Herein, we report the toluene methylation coupled with CO hydrogenation to showcase an enhancement in para-xylene (PX) selectivity by employing a bifunctional catalyst composed of ZnZrOx (ZZO) and modified Z5. The results showed that a PX selectivity of up to 81.8% in xylene and xylene selectivity of 64.8% in hydrocarbons at 10.3% toluene conversion can be realized over the bifunctional catalyst on a fixed-bed reactor. The selectivity of gaseous hydrocarbons decreased to 10.9%, and approximately half of that was observed in methanol reagent route where the PX selectivity in xylene was 38.8%. We observed that the acid strength, the quantity ratio of Brönsted and Lewis acid sites, and the pore size of zeolites were essential for the PX selectivity. The investigation of the H2/D2 kinetic isotope effect revealed that the newborn methyl group in xylene resulted from the hydrogenation of CO rather than toluene disproportionation. Furthermore, the catalyst showed no evident deactivation within the 100 h stability test. The findings offer a promising route for the production of value-added PX with high selectivity via toluene methylation coupled with syngas conversion.

    Simultaneous hydrogen production with the selective oxidation of benzyl alcohol to benzaldehyde by a noble-metal-free photocatalyst VC/CdS nanowires
    Muhammad Tayyab, Yujie Liu, Shixiong Min, Rana Muhammad Irfan, Qiaohong Zhu, Liang Zhou, Juying Lei, Jinlong Zhang
    2022, 43 (4):  1165-1175.  DOI: 10.1016/S1872-2067(21)63997-9
    Abstract ( 427 )   HTML ( 13 )   PDF (2906KB) ( 269 )  
    Supporting Information

    In this work we used CdS NWs (nanowires) with vanadium carbide (VC) attached via facile electrostatic self-assembly and calcination method. The results showed that compared to pristine CdS NWs, the photocatalytic activity of CdS NWs loaded with the particular amount of VC was dramatically enhanced. Among them, the VC/CS-15 indicated the highest enhancement for simultaneous production of H2 with selective oxidation of benzyl alcohol (BO) into benzaldehyde (BD). The highest hydrogen evolution rate of 20.5 mmol g-1h-1was obtained with more than 99% selectivity for BD production under visible light (λ ˃ 420 nm) irradiation for 2 h, which was almost 661 times higher than the pristine CdS NWs. This enhancement of photocatalytic activity is due to the VC, which provides a favorable attraction for BO by lowering the zeta potential, along with the active site for hydrogen production, and retard the recombination of electron-hole pairs by increasing the conductivity of the photocatalyst. Moreover, the apparent quantum efficiency (AQE) of VC/CS-15 for BD and H2 production at monochromatic 420 nm is about 7.5%. At the end of the hydrogen evolution test, the selective oxidation with more than 99% selectivity was obtained. It hopes this work will prove its future significance and move scientific community toward a more economical way for achieving the commercialization of H2 by photocatalysis.

    A MOF derived hierarchically porous 3D N-CoPx/Ni2P electrode for accelerating hydrogen evolution at high current densities
    Lan Wang, Ning gong, Zhou Zhou, Qicheng Zhang, Wenchao Peng, Yang Li, Fengbao Zhang, Xiaobin Fan*
    2022, 43 (4):  1176-1183.  DOI: 10.1016/S1872-2067(21)63982-7
    Abstract ( 130 )   HTML ( 7 )   PDF (2403KB) ( 271 )  
    Supporting Information

    Hydrogen evolution reaction is a critical reaction in water splitting for hydrogen production. However, developing effective and stable non-noble-metal electrocatalysts which work well at high current densities demanded by industry still remain great challenge. Herein, taking advantage of the highly tunable metal-organic framework (MOF) templates, nitrogen doped binary transition metal phosphides electrocatalysts (N-CoPx/Ni2P) with three-dimensional (3D) conductive network structure were successfully synthesized. The 3D open porous channels could expose more catalytically active sites; nitrogen doping and the synergistic effect between CoP and Ni2P can increase the electron density of Co atoms at active sites, further optimizing the Gibbs free energy of hydrogen (ΔGH*) and water (ΔGH2O*). As a result, the obtained N-CoPx/Ni2P catalyst exhibits extraordinary electrocatalytic activity in a wide pH range. Especially, it requires an extremely low overpotential of 152 mV to deliver a high current density of 650 mA cm-2in alkaline media. This work may shed some light on the rational design of cheap electrocatalysts and electrode materials that work well at high current densities.

    Pickering interfacial biocatalysis with enhanced diffusion processes for CO2 mineralization
    Boyu Zhang, Jiafu Shi, Yang Zhao, Han Wang, Ziyi Chu, Yu Chen, Zhenhua Wu, Zhongyi Jiang
    2022, 43 (4):  1184-1191.  DOI: 10.1016/S1872-2067(21)63998-0
    Abstract ( 146 )   HTML ( 15 )   PDF (1570KB) ( 161 )  
    Supporting Information

    Utilization of carbon dioxide (CO2) has become a crucial and anticipated solution to address environmental and ecological issues. Enzymes such as carbonic anhydrase (CA) can efficiently convert CO2 into various platform chemicals under ambient conditions, which offers a promising way for CO2 utilization. Herein, we constructed a Pickering interfacial biocatalytic system (PIBS) stabilized by CA-embedded MOFs (ZIF-8 and ZIF-L) for CO2 mineralization. Through structure engineering of MOFs and incorporation of Pickering emulsion, the internal and external diffusion processes of CO2 during the enzymatic mineralization were greatly intensified. When CO2 was ventilated at a flow rate of 50 mL min-1for 1 h, the pH value of PIBS dropped from ~8.00 to ~6.50, while the average pH value of free system only dropped to ~7.15, indicating that the initial reaction rate of CO2 mineralization of PIBS is nearly twice that of the free system. After the 8thcycle reaction, PIBS can still produce more than 9.8 mg of CaCO3 in 5 min, realizing efficient and continuous mineralization of CO2.