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Chinese Journal of Catalysis
2023, Vol. 49
Online: 18 June 2023

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Cover: Professor Shuang-Feng Yin and coworkers provided a systematic review of the research progress on the heterogeneous photocatalytic oxidation of benzene to phenol, including photocatalyst design principles, modification strategies, reaction mechanisms, factors influencing reaction kinetics, reactor design, and photocatalyst deactivation mechanisms, etc. Read more about the article behind the cover on page 16–41.

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Controllable synthesis of dual-atom catalysts by a confinement-pyrolysis strategy Jingyi Han, Jingqi Guan 2023, 49:  1-4.  DOI: 10.1016/S1872-2067(23)64436-5 Abstract ( 702 )   HTML ( 30 )   PDF (931KB) ( 391 )

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Using the femtosecond technique to study charge transfer dynamics Junjiang Zhu, S. Wageh, Ahmed A. Al-Ghamdi 2023, 49:  5-7.  DOI: 10.1016/S1872-2067(23)64438-9 Abstract ( 420 )   HTML ( 26 )   PDF (1475KB) ( 296 )

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Click chemistry as a connection tool: Grand opportunities and challenges Chen Wang, Junzhu Yang, Yuan Lu 2023, 49:  8-15.  DOI: 10.1016/S1872-2067(23)64434-1 Abstract ( 598 )   HTML ( 26 )   PDF (1661KB) ( 409 )   Although the concept of click chemistry was proposed more than twenty years ago, the research progress of click chemistry has emerged with great vitality, and this year's Nobel Prize in chemistry has once again highlighted the importance of the field of click chemistry. Click chemistry is a reaction in which a variety of molecules are quickly and reliably synthesized by piecing together small units. In particular, it emphasizes the development of new combinatorial chemistry methods based on the synthesis of carbon-heteroatomic bonds and the simple and efficient acquisition of molecular diversity through these reactions. Based on the superior reaction characteristics of click chemistry, click chemistry methods for production are advancing toward precision, simplicity, and high returns, especially in producing polymer materials and some bright biomedical applications. Here, we describe the development logic of typical click reactions with different substrates and catalysts. The latest technologies of click chemistry in the structure control and functional properties of polymers, as well as in the field of biomedicine and its expanding applications, are discussed. Finally, we identify the challenges of click chemistry in reaction mechanisms and engineering applications, and suggest potential future development directions in the future.

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Research progress on the heterogeneous photocatalytic selective oxidation of benzene to phenol Mengistu Tulu Gonfa, Sheng Shen, Lang Chen, Biao Hu, Wei Zhou, Zhang-Jun Bai, Chak-Tong Au, Shuang-Feng Yin 2023, 49:  16-41.  DOI: 10.1016/S1872-2067(23)64430-4 Abstract ( 583 )   HTML ( 31 )   PDF (6977KB) ( 307 )   Phenol is important for the manufacture of phenolic chemicals. The current cumene process for phenol production requires harsh conditions and suffers from unwanted side products. Nowadays, the one step conversion of benzene to phenol has received much attention. However, because of the obscurity in benzene C(sp2)-H bond activation and the easy oxidation of phenol, the direct oxidation of benzene to phenol is challenging. As an alternative, the photocatalytic selective oxidation of benzene into phenol under mild conditions is considered promising. In this review, we systematically summarize the recent advance of heterogeneous photocatalytic oxidation of benzene, including those of design principles and various modification strategies, mechanistic understanding determined based on in situ characterization and density functional theory calculation, factors affecting kinetics of the reaction, reactor design and photocatalyst deactivation. It is envisaged that photocatalysts made up of single atoms, layered double hydroxides, and metal clusters are good candidates. At the end of this article, the perspective of catalyst design and strategies for the exploration of reaction mechanism are discussed, emphasizing on the use of state-of-the-art techniques. Moreover, the design of photocatalytic reactors for the realization of the photocatalytic process is considered.

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Metal-sulfide-based heterojunction photocatalysts: Principles, impact, applications, and in-situ characterization Haibo Zhang, Zhongliao Wang, Jinfeng Zhang, Kai Dai 2023, 49:  42-67.  DOI: 10.1016/S1872-2067(23)64444-4 Abstract ( 1138 )   HTML ( 83 )   PDF (12088KB) ( 728 )   Semiconductor photocatalysis is a new sustainable development technology that has demonstrated remarkable potential in the fields of energy-production and environmental-protection. However, a single photocatalyst usually does not possess both strong redox and fast charge-separation properties, greatly limiting photocatalysis efficiency. Heterojunction photocatalysts can perfectly solve this problem by providing multiple reactive sites and fast charge separation and migration, elevating photocatalytic efficiency to a new higher level. Metal sulfides are a family of compounds composed of metals and sulfur (e.g., CdS, CuS, MoS2, In2S3, ZnIn2S4, and ZnxCd1-xS) that are preferred choices for heterojunction photocatalysts due to their narrow bandgaps, broad visible-light absorption ranges, and convenient preparation methods. This review article introduces the characteristics of metal sulfides, summarizes methods for their synthesis, and discusses various types of metal-sulfide-based heterojunctions. The use of such photocatalysts in energy and environmental-remediation applications is subsequently discussed. In addition, the roles of charge separation and transfer in heterojunction photocatalysts are demonstrated using in-situ characterization techniques. Finally, we discuss some application prospects and challenges concerning metal-sulfide-based heterojunction photocatalysts.

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Non-oxidative coupling of methane over Mo-doped CeO2 catalysts: Understanding surface and gas-phase processes Hao Zhang, Yaqiong Su, Nikolay Kosinov, Emiel J. M. Hensen 2023, 49:  68-80.  DOI: 10.1016/S1872-2067(23)64440-7 Abstract ( 338 )   HTML ( 16 )   PDF (9882KB) ( 151 )   Supporting Information Direct catalytic non-oxidative coupling is a promising route for the valorization of abundant methane. Understanding the mechanism is difficult because reactions at the surface of the catalyst and in the gas phase via radicals are important at the high temperatures employed. Herein, a series of Mo-doped CeO2 samples with isolated Mo sites were prepared by flame spray pyrolysis method and screened for their performance in non-oxidative coupling of methane. The selectivity to value-added C2 hydrocarbons (ethane and ethylene) among gas-phase products could reach 98%. During the reaction, the isolated Mo-oxo species in the as-prepared catalyst are reduced and convert into Mo (oxy-)carbide species, which act as the active sites for methane activation. By varying the available catalyst-free gas volume along the length of the reactor, we studied the contribution of gas-phase reactions in the formation of different products. Ethane is the primary product of non-oxidative methane coupling and, at least, a part of ethylene and most of benzene is formed through gas-phase chemistry. This work provides insights into the design of efficient catalysts for non-oxidative coupling of methane and highlights the importance of reducing the free volume in the reactor to limit secondary gas-phase reactions.

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Introduction of aromatic amino acids in electron transfer pathways yielded improved catalytic performance of cytochrome P450s Shuaiqi Meng, Zhongyu Li, Yu Ji, Anna Joelle Ruff, Luo Liu, Mehdi D. Davari, Ulrich Schwaneberg 2023, 49:  81-90.  DOI: 10.1016/S1872-2067(23)64445-6 Abstract ( 356 )   HTML ( 21 )   PDF (9839KB) ( 170 )   Supporting Information Cytochrome P450s are versatile catalysts for biosynthesis applications. In the P450 catalytic cycle, two electrons are required to reduce the heme iron and activate the subsequent reductions through proposed electron transfer pathways (eTPs), which often represent the rate-limiting step in reactions. Herein, the P450 BM3 from Bacillus megaterium was engineered for improved catalytic performance by redesigning proposed eTPs. By introducing aromatic amino acids on eTPs of P450 BM3, the “best” variant P2H02 (A399Y/Q403F) showed 13.9-fold improved catalytic efficiency (kcat/KM = 913.5 L mol‒1 s‒1) compared with P450 BM3 WT (kcat/KM = 65.8 L mol‒1 s‒1). Molecular dynamics simulations and electron hopping pathways analysis revealed that aromatic amino acid substitutions bridging the cofactor flavin mononucleotide and heme iron could increase electron transfer rates and improve catalytic performance. Moreover, the introduction of tyrosines showed positive effects on catalytic efficiency by potentially protecting P450 from oxidative damage. In essence, engineering of eTPs by aromatic amino acid substitutions represents a powerful approach to design catalytically efficient P450s (such as CYP116B3) and could be expanded to other oxidoreductases relying on long-range electron transfer pathways.

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Ethanol dehydrogenation to acetaldehyde over a Cuδ+-based Cu-MFI catalyst Xianquan Li, Jifeng Pang, Yujia Zhao, Pengfei Wu, Wenguang Yu, Peifang Yan, Yang Su, Mingyuan Zheng 2023, 49:  91-101.  DOI: 10.1016/S1872-2067(23)64431-6 Abstract ( 350 )   HTML ( 15 )   PDF (3695KB) ( 198 )   Supporting Information Copper catalysts have been extensively investigated for the dehydrogenation of ethanol to acetaldehyde. However, identifying the essential active sites for this reaction is difficult because of the complex coordination structure and variable valences of the Cu species during the reaction. The stability of the Cu catalysts in the reaction also needs to be substantially improved. In this study, Cu-MFI, a well-defined Cu-based Lewis acid catalyst, was prepared using a post-acid treatment method for ethanol dehydrogenation. Different from the widely reported Cu+ and Cu0 species accounting for the activity of Cu catalysts, conditional experiments and in situ characterizations revealed that the highly dispersed Cuδ+ (1 < δ < 2) species on the MFI support are the essential active sites for ethanol dehydrogenation. Due to the strong interaction between Cu and silica via the Cu-O-Si linkage, the Cuδ+ species were very stable in the reaction and played the role of a Lewis acid catalyst in promoting ethanol activation and dehydrogenation. Over the optimal catalyst 5%Cu-MFI-deCu, 95% selectivity of acetaldehyde and approximately 87% ethanol conversion were obtained at 250 °C and a weight hourly space velocity of 0.64 h−1 in 120 h time on stream.

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Ultrathin ZnTi-LDH nanosheet: A bifunctional Lewis and Brönsted acid photocatalyst for synthesis of N-benzylideneanilline via a tandem reaction Cheng Liu, Mengning Chen, Yingzhang Shi, Zhiwen Wang, Wei Guo, Sen Lin, Jinhong Bi, Ling Wu 2023, 49:  102-112.  DOI: 10.1016/S1872-2067(23)64449-3 Abstract ( 257 )   HTML ( 10 )   PDF (5446KB) ( 130 )   Supporting Information Two ultrathin ZnTi-LDH nanosheets with different thickness (1.4 and 4.0 nm) were prepared to study the interplay between the active site and catalytic performance in photocatalytic synthesis of N-benzylideneanilline via a tandem reaction. ZnTi-LDH nanosheet possesses dual isolated active sites including the coordinatively unsaturated Ti atoms (Lewis acid sites) and the H atoms of OH groups (Brönsted acid sites), achieving the activation of benzyl alcohol and nitrobenzene via C-O···Ti species and N-O···H-O species, respectively. Photogenerated holes and electrons facilitate the oxidation of benzyl alcohol to benzaldehyde and the reduction of nitrobenzene to aniline, respectively. The thinner sample possesses more active sites, facilitating not only the activation of reactants but also the separation of photogenerated carriers. Therefore, a thinner ZnTi-LDH nanosheet shows the high conversion (100%) and the high selectivity (96%). Finally, a synergetic photocatalytic mechanism connected to the molecular activation is illustrated at the molecule level.

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Highly efficient photothermal catalytic upcycling of polyethylene terephthalate via boosted localized heating Xiangxi Lou, Xuan Gao, Yu Liu, Mingyu Chu, Congyang Zhang, Yinghua Qiu, Wenxiu Yang, Muhan Cao, Guiling Wang, Qiao Zhang, Jinxing Chen 2023, 49:  113-122.  DOI: 10.1016/S1872-2067(23)64435-3 Abstract ( 491 )   HTML ( 28 )   PDF (3294KB) ( 428 )   Supporting Information Photothermal catalysis driven by clean solar energy efficiently converts plastic waste into high-value-added products. The catalytic process involves the transformation of solar energy to chemical energy. However, designing photothermal catalysts with a high conversion efficiency and catalytic activity remains considerably challenging. In this study, a c-ZIF-8@SiO2 nanostructure is fabricated. It acts both as the photothermal reagent and the catalyst, displaying high photothermal conversion efficiency, catalytic activity, and stability in polyethylene terephthalate (PET) glycolysis. SiO2-coated c-ZIF-8 effectively reduces the thermal radiation loss of the carbon material, thus enhancing the local thermal effect of the catalytic system. Consequently, the conversion efficiency of PET achieved using photothermal catalysis is 3.4 times higher than that of thermal catalysis under the same conditions. An economic efficiency analysis proves that photothermal catalysis can save 6390000 kW·h of electricity and reduce up to 3089.59 tons of CO2 emissions for every 10000 tons of PET recycled. Therefore, the development of clean energy-driven photothermal catalysis technology could be a potential solution for the upcycling of waste plastics.

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Ni-catalyzed unnatural prenylation and cyclic monoterpenation of heteroarenes with isoprene Gong Zhang, Wei-Song Zhang, Xiao-Yu Wang, Yang Yang, Ding-Wei Ji, Boshun Wan, Qing-An Chen 2023, 49:  123-131.  DOI: 10.1016/S1872-2067(23)64437-7 Abstract ( 150 )   HTML ( 5 )   PDF (913KB) ( 92 )   Supporting Information Terpenoids, such as hemiterpenoids and monoterpenoids, are the largest class of natural products, which widely exist in plants and marine organisms. Herein, a divergent strategy is developed for the introduction of unnatural prenyl and cyclic monoterpene skeleton through relay catalysis from basic feedstock isoprene. In the presence of catalytic amount of base, the unnatural prenylation of heteroarenes proceeds through Markovnikov addition onto isoprene with less hindered NHC (IMes) ligand under Ni catalysis. With the aid of extra base, a further in situ isomerization of Markovnikov addition products delivered unnatural hemiterpenoids with tetrasubstituted alkene motif in high selectivities. It was found that bulky NHC (IPr) ligand could further promote sequential hydroheteroarylation between isoprene dimers and heterocycles and gave monoterpenoids in one pot. This work provides a new strategy for regulating the synthesis of hemiterpenoids and monoterpenoids.

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B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO2RR Jiao Wang, Fangfang Zhu, Biyi Chen, Shuang Deng, Bochen Hu, Hong Liu, Meng Wu, Jinhui Hao, Longhua Li, Weidong Shi 2023, 49:  132-140.  DOI: 10.1016/S1872-2067(23)64443-2 Abstract ( 481 )   HTML ( 16 )   PDF (5165KB) ( 153 )   Supporting Information The accuracy and efficiency tuning the local electronic structure of catalyst active sites are pre-requisites for achieving high selectivity CO2 reduction reaction on a wide potential window, whereas remain a great challenge. Here, a B-doped CuIn alloy catalyst with tunable electronic structure for the highly effective electrochemical conversion of CO2 to CO has been exploited. The obtained B-doped CuIn alloy performs an optimal CO Faraday efficiency of 99% at -0.6 V (vs. the reversible hydrogen electrode) and particularly keeps outstanding CO Faraday efficiency (> 90%) over a wide cathodic electrochemical window (400 mV). Density functional theory theoretical calculation manifests that the enhanced performance is primarily ascribed to the electron-capturing ability of high valence state B atom, which optimizes the local electronic structure of adjacent metal active sites and adjusts the binding energy between catalyst and intermediates. A foundation of designing advanced electrochemical CO2 reduction reaction catalysts can be served by the insights gained though this research.

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Phosphate-decorated Fe-N-C to promote electrocatalytic oxygen reaction activities for highly stable zinc-air batteries Guangying Zhang, Xu Liu, Xinxin Zhang, Zhijian Liang, Gengyu Xing, Bin Cai, Di Shen, Lei Wang, Honggang Fu 2023, 49:  141-151.  DOI: 10.1016/S1872-2067(23)64432-8 Abstract ( 274 )   HTML ( 12 )   PDF (5520KB) ( 272 )   Supporting Information An obvious challenge for rechargeable Zn-air batteries (ZABs) is the impact of large charge potentials on the oxidation of their cathode catalysts, which accelerates the corrosion of the carbon electrodes, and significantly compromises their stability. It is therefore necessary to design simple methods aimed at facilitating the oxygen evolution reaction (OER) processes of ZABs to suppress the corrosion of their cathode materials. Herein, a biomass-derived N-doped porous carbon material coupled with Fe3O4 and Fe2N nanoparticles and modified with phosphorus (P-Fe3O4/Fe2N@NPC) was designed as an air-cathode to reduce the charging voltage of ZABs. It exhibited excellent ORR/OER bifunctional electrocatalytic activities, and the assembled ZAB displayed an ultra-long service life. DFT calculations showed that the P-modification modulated the electronic state and coordination environment of the active iron atom, thereby significantly enhancing the OER activity of P-Fe3O4/Fe2N@NPC.

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The crystalline linear polyimide with oriented photogenerated electron delivery powering CO2 reduction Huizhen Li, Yanlei Chen, Qing Niu, Xiaofeng Wang, Zheyuan Liu, Jinhong Bi, Yan Yu, Liuyi Li 2023, 49:  152-159.  DOI: 10.1016/S1872-2067(23)64450-X Abstract ( 266 )   HTML ( 13 )   PDF (3227KB) ( 128 )   Supporting Information Orienting electron transport to suppress charge recombination is attractive for efficient photocatalysis but remains challenging. Herein, we demonstrate the synthesis of crystalline linear conjugated polyimides via the condensation of carboxylic anhydrides and amine monomers for the photocatalytic reduction of CO2. Oriented electron transport was achieved using crystalline polyimides integrated with electronic push-pull units. Directional intramolecular electron transfer is driven by the dipole effects of the adjacent building units. The sulfone-based polyimide exhibited excellent photocatalytic performance for CO2 reduction. Our work provides a new example photoreduction of CO2 and a strategy for developing efficient photocatalysts with oriented electron transport.

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Enhancing CO2 photoreduction via the perfluorination of Co(II) phthalocyanine catalysts in a noble-metal-free system Zizi Li, Jia-Wei Wang, Yanjun Huang, Gangfeng Ouyang 2023, 49:  160-167.  DOI: 10.1016/S1872-2067(23)64433-X Abstract ( 407 )   HTML ( 10 )   PDF (2508KB) ( 163 )   Supporting Information The manufacture of high-performance photocatalytic systems based on earth-abundant elements remains a key challenge, urging operative strategies for catalyst design. Herein, we present the construction of an efficient and noble-metal-free molecular system for the photoreduction of CO2 to CO using a Cu(I) photosensitizer and Co(II) phthalocyanine catalysts. It was found that the perfluorination of Co(II) phthalocyanine shows enhanced catalytic performance for CO2-to-CO conversion compared with pristine Co(II) phthalocyanines, achieving a remarkable apparent quantum yield of 58.2% at 425 nm, which is three times that of the pristine one (19.0%). The Cu(I)/Co(II) system also achieved a maximum turnover number of 9185 and near-unity selectivity. These improvements can be attributed to the electron-withdrawing effect of the fluorine substituents, which lowers the catalytic overpotential for catalysis and decreases the Gibbs free energy of the rate-determining Co-carboxylate-forming step. This work indicates that perfluorination is an effective approach to optimize the catalytic performance of molecular catalysts.

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NH3 synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H2O over Cu/CeO2 Xinjie Song, Shipeng Fan, Zehua Cai, Zhou Yang, Xun Chen, Xianzhi Fu, Wenxin Dai 2023, 49:  168-179.  DOI: 10.1016/S1872-2067(23)64439-0 Abstract ( 270 )   HTML ( 9 )   PDF (4197KB) ( 398 )   Supporting Information A photothermal catalytic system comprising Cu/CeO2 was applied to the reaction between NO, CO and H2O for the production of NH3 under visible-light irradiation. High NO conversion (94.4%) and NH3 selectivity (66.5%) were achieved over Cu/CeO2 in the presence of H2O at 210 °C. Visible light further improved the conversion of NO (97.7%) and selectivity for NH3 (69.1%). The quasi-situ EPR and in-situ DRIFTS results indicated that CO initially reacts with H2O to form an HCO3* intermediate, which then decomposes into CO2 and activated H*. Finally, NO reacts with activated H* to produce NH3. The localized surface plasmon resonance effect of Cu nanoparticles induced by visible light promotes the decomposition of HCO3* to CO2 and H*, while regenerating oxygen vacancies (OVs, H2O activation sites) at the CeO2 sites, resulting in enhanced NH3 production. This study offers a convenient approach for NH3 production under mild conditions.

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Size-dependent electronic interface effect of Pd nanocube-based heterojunctions on universally boosting phenol hydrogenation reactions Si-Yuan Xia, Qi-Yuan Li, Shi-Nan Zhang, Dong Xu, Xiu Lin, Lu-Han Sun, Jingsan Xu, Jie-Sheng Chen, Guo-Dong Li, Xin-Hao Li 2023, 49:  180-187.  DOI: 10.1016/S1872-2067(23)64442-0 Abstract ( 194 )   HTML ( 11 )   PDF (6630KB) ( 102 )   Supporting Information As mainstream catalysts for phenol hydrogenation with good reusability and high selectivity under mild conditions, Pt- and Pd-based heterogeneous catalysts suffer from unsatisfied catalyst costs. The structures of metals (i.e., particle sizes, alloy structures, and porosity) and the acidity of the support were optimized to boost the intrinsic activity of noble metal nanocatalysts with a maximum promoting factor of 3.3. There is considerable scope for exploring more powerful methods for boosting the mass activity of metal catalysts. Herein, we demonstrate a novel size-dependent electronic interface effect in the heterojunctions of Pd nanocubes and sulfur-doped carbon (SC) supports to enhance phenol hydrogenation activity. Theoretical calculations and experimental results indicate that the size-dependent electron deficiency of Pd nanocubes on the designed SCs as electron acceptors results in an unexpected and universal promotion of phenol hydrogenation activity, outperforming free-standing Pd nanocubes by a factor of 9-19.