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Chinese Journal of Catalysis
2024, Vol. 60
Online: 18 May 2024

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Cover: The research group headed by Associate Professor Yi Zhan at Sun Yat-sen University has developed a bifunctional oxygen catalyst named KB@Co-C₃N₄. This catalyst utilizes g-C₃N₄ to anchor Co-N_x active sites while simultaneously coating Ketjenblack (KB) to form a wonton-like structure. This unique design not only enhances the Co-N_x active sites but also protects KB from carbon corrosion. The resulting catalyst exhibits significant catalytic activity and robust stability in the neutral electrolytes, making it a promising candidate for zinc-air batteries operating in neutral media. Read more about the article behind the cover on page 178–189.

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Account of doping photocatalyst for water splitting Wenjian Fang, Jiawei Yan, Zhidong Wei, Junying Liu, Weiqi Guo, Zhi Jiang, Wenfeng Shangguan 2024, 60:  1-24.  DOI: 10.1016/S1872-2067(23)64637-6 Abstract ( 307 )   HTML ( 44 )   PDF (16711KB) ( 199 )   In the field of photocatalytic water splitting, the strategy of doping photocatalysts has emerged as a significant and extensively studied approach. Doping can effectively facilitate the modification of both the microstructure and energy band structure of the photocatalyst, addressing key performance limitations such as light absorption, position of the conduction and valence band minima (CBM and VBM), photogenerated carrier separation, and surface chemical reactions. In recent years, we have reported several works about the doping of rare earth elements into bismuth-based composite oxides. These endeavors are aimed at enhancing the conduction band minimum and achieving overall water splitting under visible light. Based on these bismuth-based composite oxides, we studied the effects of doping on the microstructures of photocatalysts, including exposed surfaces, surface properties, and defects. Recently, we introduce an innovative asymmetric doping technique—Selected Local Gradient Doping, intricately placing doped ions within nanocapsules. This approach allows for the gradual, controlled, and localized release of doped ions to the primary photocatalyst. Therefore, this account is to review our related research in the field of doping for photocatalytic water splitting. The primary focus on doping bismuth-based composite oxides and Asymmetry doping would significantly make contribution to the exploration of novel materials for photocatalytic water splitting under visible light and the enhancement of energy conversion efficiency.

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Rational design and mechanistic insights of advanced photocatalysts for CO2-to-C2+ production: Status and challenges Chenyu Du, Jianping Sheng, Fengyi Zhong, Ye He, Vitaliy P. Guro, Yanjuan Sun, Fan Dong 2024, 60:  25-41.  DOI: 10.1016/S1872-2067(23)64642-X Abstract ( 780 )   HTML ( 62 )   PDF (4693KB) ( 309 )   Photocatalytic CO2 conversion into high-value chemicals is becoming an increasingly promising avenue of research in the quest for sustainable carbon resource utilization. Particularly, compounds with two or more carbons (C2+) have higher added value than methane, carbon monoxide, or formate, which are typically the major products of CO2 reduction. In this review, we present a detailed account of recent advancements in the field of photocatalytic CO2 conversion, with a specific focus on the synthesis of multi-carbon oxygenates. We systematically introduce the rational design of photocatalysts with high effectivity and selectivity, which follows a methodical inside-to-outside order. These strategies consider various aspects of photocatalyst optimization, from the core structure to the surface properties. Meanwhile, we delve into an in-depth analysis of the underlying catalytic mechanisms, particularly emphasizing the C-C coupling and multi-electron-coupled proton transfer processes. Lastly, we examine the prospects and challenges in developing photocatalysts for CO2 conversion, providing valuable insights for researchers and practitioners. This review aims to serve as a valuable resource for those seeking to design advanced catalysts for efficient photocatalytic CO2 reduction.

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Ammonia electrosynthesis on carbon-supported metal single-atom catalysts Mu-Lin Li, Yi-Meng Xie, Jingting Song, Ji Yang, Jin-Chao Dong, Jian-Feng Li 2024, 60:  42-67.  DOI: 10.1016/S1872-2067(24)60032-X Abstract ( 300 )   HTML ( 25 )   PDF (11890KB) ( 137 )   Ammonia, a feedstock platform for fertilizer and pharmaceutical production, is regarded as a zero-carbon energy carrier. The electrochemical synthesis of ammonia, powered by clean and renewable electricity, has garnered increased attention as an alternative to the Haber-Bosch process. Very recently, single-atom catalysts (SACs) have become highly effective electrocatalysts for such electrochemical transformation, where the isolated metal sites ensure the high atomic utilization efficiency as well as the prevention of nitrogen-nitrogen coupling. In this review, we focus on the recent progress of single-atom catalysts in electrochemical ammonia synthesis and briefly introduce nitrogen cycles in both natural and artificial ecosystems, followed by a discussion of catalyst design by theoretical and experimental methods. Synthesis routes from different nitrogen sources, including dinitrogen (N2) and nitrogen oxides (NOx), are also highlighted. Besides, the catalysis dynamics as an indispensable section is presented and discussed in-depth. Finally, we tackle challenges and offer perspectives, aspiring to provide insightful guidance for researchers in this community striving for advanced ammonia electrosynthesis.

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A review on fundamentals for designing stable ruthenium-based catalysts for the hydrogen and oxygen evolution reactions Wangyan Gou, Yichen Wang, Mingkai Zhang, Xiaohe Tan, Yuanyuan Ma, Yongquan Qu 2024, 60:  68-106.  DOI: 10.1016/S1872-2067(24)60013-6 Abstract ( 387 )   HTML ( 30 )   PDF (39464KB) ( 154 )   Clean and renewable energy is generally localized and intermittent. Thus, energy conversion and storage technologies are necessary to compensate for these shortcomings. Electrolytic water splitting presents a reliable and promising energy technology for producing high purity hydrogen (H2). Among the platinum metals, ruthenium (Ru) has gained significant attentions as it generally outperforms commercial catalysts in terms of activity at a more affordable price. Although great progress has been made in improving the catalytic activity of Ru-based catalysts, stability remains a major challenge hindering their practical applications. To this end, this review introduces the fundamentals of the stability over Ru-based catalysts for water splitting, including the reaction mechanisms of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), measurement methods and evaluation criteria, as well as deactivation mechanisms. Moreover, the up-to-date advances of representative strategies for improving HER and OER stability of Ru-based catalysts are further discussed with respect to specific design principles and underlying mechanisms. Ultimately, insights into the challenges and opportunities for Ru-based electrocatalysts are provided to promote the development of next-generation Ru-based catalysts with exceptional stability. This review aims at guiding the design and synthesis of superior catalysts, generating increased interest among researchers, and stimulating further advanced research.

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Recent progress in electrocatalytic reduction of nitrogen to ammonia Guangtong Hai, Zhongheng Fu, Xin Liu, Xiubing Huang 2024, 60:  107-127.  DOI: 10.1016/S1872-2067(23)64640-6 Abstract ( 476 )   HTML ( 39 )   PDF (7654KB) ( 200 )   Nitrogen reduction reaction (NRR) plays a vital role in the nitrogen cycling within ecosystems, agricultural systems, and industrial applications. Suffering from the low solubility of nitrogen (N2), high stability of N≡N triple bond and severe competitive hydrogen evolution reaction (HER), electrochemical NRR currently faces several problems such as sluggish yield rate and low Faraday efficiency (FE). So far, dedicated endeavors have led to significant advancements in NRR, but it is still far from satisfactory now. In this comprehensive review, we systematically consolidate recent advancements in electrochemical NRR, including high-performance NRR catalysts, innovative NRR reaction equipment, and the regulation and optimization of NRR reaction pathways. More importantly, from the reported researches, we proposed that the improvement of NRR performance required coordinated regulation from many aspects, and the unitary aspect of optimization is difficult to break through the existing bottleneck. Therefore, unlike other recent reviews, we didn’t discuss in chronological order here, but with three subsections according to these aspects. In the outlook section, we highlighted the existing challenges within the NRR field. This review would serve as a guiding framework for the strategic design of catalysts and devices in NRR, while also contributing to the refinement and optimization of NRR mechanisms.

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Review on recent advances in phase change materials for enhancing the catalytic process Chang’an Wang, Ying Ouyang, Yibin Luo, Xinru Gao, Hongyi Gao, Ge Wang, Xingtian Shu 2024, 60:  128-157.  DOI: 10.1016/S1872-2067(24)60016-1 Abstract ( 228 )   HTML ( 7 )   PDF (16589KB) ( 75 )   Catalysis plays a critical role in almost every industrial process, and developing high-performance catalyst is one of the most efficient strategies for enhancing the catalytic process. However, most of the catalytic processes involve the heat release or absorption effect, which would influence the catalytic efficiency and even result in the deactivation of the catalyst. Recently, phase change materials (PCMs) have demonstrated unique potential for enhancing the catalytic process in thermocatalytic, photocatalytic, biocatalytic and electrochemical fields due to the thermal management and energy storage functions. The innovative integration of PCMs and catalysts can simultaneously raise energy efficiency and enhance the catalytic process. Microencapsulation technology enables the in-situ coupling of PCMs within catalysts, and the introduction of encapsulated shells or nanoparticles with catalytic effects endows the PCMs with good chemical stability, thermal cycling stability as well as high thermal conductivity. The synergistic mechanism between catalysts and PCMs in different systems can be summarized as self-stored thermal driven catalysis, in-situ temperature regulation and heat flow/electron synergistic effect. In addition, the correlation between the microstructure and catalytic/thermal management performance of PCMs@Catalysts composites was systematically discussed. Finally, the current challenges and development trends of the multifunctional PCMs@Catalysts composites are also presented. The review aims to highlight recent advances in phase change materials for enhancing the catalytic process and provide insights into the rational design and controllable preparation of PCMs@Catalysts composites.

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Self-healing mechanisms toward stable photoelectrochemical water splitting Chao Feng, Yanbo Li 2024, 60:  158-170.  DOI: 10.1016/S1872-2067(23)64648-0 Abstract ( 152 )   HTML ( 5 )   PDF (5427KB) ( 45 )   Achieving stability poses a significant challenge in the practical implementation of photoelectrochemical (PEC) water splitting. The main factors affecting the long-term stability of PEC devices are chemical- and photo-corrosion of the semiconductor light absorbers, along with damage to the surface protection layer and the loss or reconstruction of the active centers of the co-catalysts. Introducing the concept of self-healing provides new strategies to enhance the stability of the semiconductor light absorbers, protection layer and co-catalysts in PEC water-splitting studies. Continuous exploration of these dynamic repair strategies is expected to promote the long-term stability of the PEC devices. This review outlines the deactivation mechanisms of different semiconductor light absorbers, protection layers, and co-catalysts under operational conditions. We further highlight corresponding regeneration and repair strategies, while addressing the challenges and prospects associated with constructing self-healing stable PEC water-splitting systems.

Communication

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A general palladium-catalyzed carbonylative synthesis of α-CF3-substituted ketones and carboxylic acid derivatives Zhi-Peng Bao, Nai-Xian Sun, Xiao-Feng Wu 2024, 60:  171-177.  DOI: 10.1016/S1872-2067(23)64623-6 Abstract ( 167 )   HTML ( 15 )   PDF (1063KB) ( 59 )   Supporting Information α-CF3-substituted carboxylic acid derivatives have drawn wide attention owing to their importance for both pharmaceutical and synthetic communities. However, methodologies for their construction are still very limited. Herein, we developed a general palladium-catalyzed carbonylative procedure for the synthesis of α-CF3-substituted ketones and carboxylic acid derivatives. With amines, phenols, alcohols, arylboronic acids, and even less-nucleophilic sulfonamides and amides as the reaction partners, the corresponding amides, esters, ketones and imides were obtained in good yields with excellent functional group tolerance. Furthermore, this protocol has also been applied to the late-stage modification of 25 densely functionalized pharmaceutical agents and natural products.

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Wonton-structured KB@Co-C3N4 as a highly active and stable oxygen catalyst in neutral electrolyte for Zinc-air battery Wei-Fan Wu, Jin-Ge Fan, Zhen-Hong Zhao, Jian-Min Pan, Jing Yang, Xingbin Yan, Yi Zhan 2024, 60:  178-189.  DOI: 10.1016/S1872-2067(24)60007-0 Abstract ( 173 )   HTML ( 18 )   PDF (3562KB) ( 72 )   Supporting Information This work addresses the challenges faced by oxygen catalysis applications in neutral media, which are hindered by sluggish kinetics and severe carbon corrosion. To overcome these issues, a bifunctional oxygen catalyst (KB@Co-C3N4) was developed by utilizing graphitic carbon nitride (g-C3N4) to support Co-Nx active sites and simultaneously to wrap Ketjen black (KB) to form a wonton structure. The resulting catalyst exhibited excellent ORR/OER activity and good stability in neutral electrolytes. The KB@Co-C3N4 catalyst demonstrated a half-wave potential (E1/2) of 0.723 V and only a 9 mV decay after 40000 cycles of ORR accelerated durability test (ADT). In terms of OER, the overpotential at 10 mA cm-2 (η10) of KB@Co-C3N4 was 550 mV, with negligible increase observed even after 20 k cycles of OER ADT. The zinc-air battery incorporating KB@Co-C3N4 exhibited superior performances over other benchmark bifunctional counterparts in open-circuit voltage (1.52 V), galvanostatic discharge/charge performance and cycling duration (985 h at 5 mA cm-2). The theoretical investigation revealed that the engineered electronic structures of the metal active sites enable precise regulation of the charge distribution of Co centers, leading to optimized adsorption and desorption of oxygenated intermediates. The high stability of the catalyst is attributed to the chemically stable C3N4, which strengthens Co-Nx active sites and protects KB against carbon corrosion by wrapping KB to form the wonton structure.

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Fine tuning the dynamic PdCx formation for enhanced acetylene semi-hydrogenation: The role of gas environment and ZnO addition Huan Chen, Zhounan Yu, Bing Yang, Yafeng Zhang, Chunxia Che, Xiaoyan Liu, Feng Zhang, Wei Han, He Wen, Aiqin Wang, Tao Zhang 2024, 60:  190-200.  DOI: 10.1016/S1872-2067(24)60033-1 Abstract ( 230 )   HTML ( 10 )   PDF (3250KB) ( 80 )   Supporting Information Palladium carbide (PdCx) has been extensively reported as active phase in acetylene semi-hydrogenation that can be dynamically formed during reaction. However, fine tuning of dynamic PdCx formation towards enhanced acetylene semi-hydrogenation is of great challenge and the dynamic insights remain elusive. In this paper, the state-of-the-art in situ characterizations have been adopted to elucidate the dynamic PdCx formation for acetylene semi-hydrogenation. The role of hydrogen atmosphere and ZnO addition in tuning the carburization process were clearly identified by in situ spectroscopies. The hydrogen in the gas environment assisted the carbon infiltration via PdHx hydrides, while the addition of ZnO suppress the carburization by the surface Zn alloy. As a result, the carbon content in PdCx can be precisely modulated by altering the hydrogen atmosphere and ZnO additives, and exhibits a linear correlation with the activity of acetylene semi-hydrogenation. The carbon insertion enriched the electron state of Pd sites in PdCx that favors the activation of hydrogen for acetylene semi-hydrogenation. This work thus provides a new route for the design of Pd catalyst for high-performance acetylene semi-hydrogenation by fine tuning the reaction environment and the degree of carburization during dynamic PdCx formation.

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Metal-free photocatalytic reduction of CO2 on a covalent organic framework-based heterostructure Haoming Huang, Qingqing Lin, Qing Niu, Jiangqi Ning, Liuyi Li, Jinhong Bi, Yan Yu 2024, 60:  201-208.  DOI: 10.1016/S1872-2067(24)60027-6 Abstract ( 257 )   HTML ( 7 )   PDF (3345KB) ( 68 )   Supporting Information Photocatalytic reduction of CO2 with H2O is thought as an environment friendly approach for sustainable development. It is highly desirable but remains challenging to develop photocatalyst with metal-free site for CO2 reduction. Here, we fabricated a heterostructure by integrating azine-based COF with ZnIn2S4, where the azine unit in COF acts as metal-free sites for CO2 adsorption and reduction. The as-formed interfused heterointerface in the heterostructure ensures the effective electron transfer from ZnIn2S4 across the interface to the COF, resulting in a spatial separation of redox sites for CO2 reduction and water oxidation. The hybrid catalyst exhibits remarkably enhanced photocatalytic activity for CO2 reduction to CO, which is 8 and 6 times than the COF and ZnIn2S4, respectively, and is even comparable with some metal-catalyzed CO2 reduction systems. This study provides a new paradigm to mimic natural photosynthesis by using metal-free site for CO2 reduction.

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Tuning clusters-metal oxide promoters electronic interaction of Ru-based catalyst for ammonia synthesis under mild conditions Tianhua Zhang, Haihui Hu, Jiaxin Li, Yinglong Gao, Lingling Li, Mingyuan Zhang, Xuanbei Peng, Yanliang Zhou, Jun Ni, Bingyu Lin, Jianxin Lin, Bing Zhu, Dongshuang Wu, Linjie Zhang, Lili Han, Lirong Zheng, Xiuyun Wang, Lilong Jiang 2024, 60:  209-218.  DOI: 10.1016/S1872-2067(23)64644-3 Abstract ( 160 )   HTML ( 8 )   PDF (3059KB) ( 43 )   Supporting Information Ammonia (NH3) is an excellent candidate for hydrogen storage and transport. However, producing NH3 under mild conditions is a long-term, arduous task. Atomic cluster catalysts (ACCs) have been shown to be effective for catalytic N2-to-NH3 conversion, opening the door to the development of efficient catalysts under mild conditions. Still, ACC formation with thermally stable catalytic sites remains a challenge because of their high surface free energy. Herein, we report anchoring Ba and/or Ce onto Ru ACCs (2 wt% Ru atomic clusters supported on N-doped carbon) to form so-called clusters-metal oxide promoters electronic interaction (CMEI) to stabilize the Ru atomic clusters. The resulting Ba/Ce/Ru ACCs significantly boost the NH3 synthesis rate to 56.2 mmolNH3 gcat-1 h-1 at 400 °C and 1 MPa, which is 7.5-fold higher than that of Ru ACC. The strengthened CMEI between the Ba/Ce and Ru atomic clusters across the Ba/Ce/Ru ACC enables electron transfer from Ba and/or Ce to Ru atomic clusters. As such, the electron-enriched Ru atom could facilitate electron transfer to N≡N bond π* orbitals, which would weaken the N≡N bond and drive the eventual conversion of N2 to NH3. This study offers insight into the role of CMEI in Ru ACCs and provides an effective approach for designing stable atomic cluster catalysts for NH3 synthesis.

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Regulation of d-band center of TiO2 through fluoride doping for enhancing photocatalytic H2O2 production activity Yanyan Zhao, Shumin Zhang, Zhen Wu, Bicheng Zhu, Guotai Sun, Jianjun Zhang 2024, 60:  219-230.  DOI: 10.1016/S1872-2067(23)64645-5 Abstract ( 326 )   HTML ( 13 )   PDF (11031KB) ( 142 )   Supporting Information Titanium dioxide (TiO2) has received extensive attention for photocatalytic hydrogen peroxide (H2O2) production, with the d-band center related to the adsorption performance, which affects the photocatalytic reaction process. Herein, an ingenious strategy to lower the antibonding-orbital occupancy in the Ti 3d orbital by fluoride ion (F‒) doping is proposed, with density functional theory calculations predicting that F-doping into TiO2 induces a non-uniform charge distribution and enables an upshift of the d-band center in F/TiO2. This manipulation provides accessible active centers with favorable d-band energy levels, which can improve the charge-transfer behavior, strengthen the interaction between the adsorbed oxygen and the photocatalyst, and reduce the adsorption energy of oxygen, eventually promoting the photocatalytic H2O2 production rate. The experimental results further confirm that a lower antibonding-orbital occupancy can intensify the adsorption of atomic oxygen at the Ti sites. Electron paramagnetic resonance experiment reveals that the presence of F‒ ions in the lattice induces the formation of Ti3+ centers that localize the extra electron needed for charge compensation. Femtosecond transient absorption (fs-TA) spectroscopy suggests that photogenerated electrons are transferred from the conduction band of F/TiO2 to the Ti3+ surface states and surface F‒ ions, expediting the separation of electrons and holes. Consequently, with F‒ doping in TiO2, the photocatalytic H2O2 production yields improved from 277 to 467 μmol·g‒1·h‒1, with ethanol as a sacrificial reagent. This study provides a new strategy for regulating the d-band center to optimize the adsorption strength between the photocatalyst and oxygen atoms and achieve enhanced photocatalytic H2O2 production performance.

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Towards highly-selective H2O2 photosynthesis: In-plane highly ordered carbon nitride nanorods with Ba atoms implantation Aiyun Meng, Xinyuan Ma, Da Wen, Wei Zhong, Shuang Zhou, Yaorong Su 2024, 60:  231-241.  DOI: 10.1016/S1872-2067(24)60008-2 Abstract ( 653 )   HTML ( 14 )   PDF (3572KB) ( 169 )   Supporting Information Graphitic carbon nitride (g-C3N4) shows great potential in photocatalytic H2O2 production. However, challenges arise from its low in-plane crystallinity and selectivity in two-electron oxygen reduction reaction (2e--ORR), greatly limiting its H2O2 photosynthesis efficiency. Herein, we develop an ingenious strategy to simultaneously increase the in-plane crystallinity and induce the highly-selective 2e--ORR by rationally designing barium (Ba) atom-implanted in-plane highly ordered g-C3N4 nanorods. The approach involves controllable synthesis of in-plane high crystallinity g-C3N4 nanorods with Ba implantation (BI-CN) using a BaCl2-mediated in-plane polymerization strategy. The unique Ba-N interaction induces the oriented polymerization of 3-s-triazine units to form well-arranged in-plane structures. Experimental and theoretical calculations clarify that the implanted Ba atoms function as positive charge centers, resulting in a Pauling-type O2 adsorption configuration. This minimizes O-O bond breaking energy, thus suppressing the four-electron oxygen reduction reaction (4e--ORR) and facilitating a highly-selective 2e--ORR pathway for efficient photocatalytic H2O2 production. Consequently, the optimized BI-CN3 photocatalyst exhibits an outstanding H2O2 production rate of as high as 353 μmol L-1 h-1, surpassing the pristine g-C3N4 by 6.1 times. This study concurrently optimizes the in-plane crystallinity and O2 adsorption sites of g-C3N4 photocatalysts for highly-selective H2O2 production, providing innovative insights for designing efficient photocatalysts with diverse applications.

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Redox-driven surface generation of highly active Pd/PdO interface boosting low-temperature methane combustion Yuanlong Tan, Yafeng Zhang, Ya Gao, Jingyuan Ma, Han Zhao, Qingqing Gu, Yang Su, Xiaoyan Xu, Aiqin Wang, Bing Yang, Guo-Xu Zhang, Xiao Yan Liu, Tao Zhang 2024, 60:  242-252.  DOI: 10.1016/S1872-2067(24)60021-5 Abstract ( 235 )   HTML ( 10 )   PDF (6277KB) ( 74 )   Supporting Information The supported Pd catalyst has been a benchmark for methane elimination. However, the active structures have been long under debate. Here, by the aberration-corrected high angle annular dark field scanning transmission electron microscopy, operando X-ray absorption spectroscopy and quasi in situ X-ray photoelectron spectroscopy, we revealed the two-dimensional metallic Pd bumps on the PdO surface (litchi-like structure) generated by the redox atmosphere under the lean condition as a highly active structure of the Pd/Al2O3 catalyst. The substantially increased Pd/PdO interfaces boost the methane combustion activity higher than the similar catalysts reported previously, and remarkably enhance the reaction rate by 15.5 and 10.7 times that of pure PdO or metallic Pd counterpart under lean condition at 300 °C, respectively. Density-functional theory calculations confirm the synergistic C-C bond activation of methane on the Pd/PdO interfaces. Our work provides new insight into the traditional understanding of the chemical state and particle size effects of the industrial Pd catalysts for methane oxidation.

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Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C3N4 catalysts with ultra-low Ni loading Hongyu Qu, Wende Hu, Xiangcheng Li, Rui Xu, Xiao Han, Junjie Li, Yiqing Lu, Yingchun Ye, Chuanming Wang, Zhendong Wang, Weimin Yang 2024, 60:  253-261.  DOI: 10.1016/S1872-2067(24)60017-3 Abstract ( 238 )   HTML ( 11 )   PDF (6502KB) ( 135 )   Supporting Information Selective hydrogenolysis of biomass-based platform compounds is of great importance for the production of chemicals and fuels. Herein, we reported that the catalyst of Ni-C3N4 supported on H2 activated carbon (HC) synthesized by a simple coordination-impregnation-pyrolysis method is efficient for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF); the yield of 94.2% can be obtained in a batch reactor and the lifetime of greater than 120 h can be achieved in fixed-bed experiment. It is demonstrated that Ni nanoparticles coated by graphitic C3N4 shell were highly dispersed on the surface of HC and the Ni loading is as low as 0.86 wt%, beneficial to the anti-sintering of Ni nanoparticles during the reaction. Both XPS characterizations and theoretical calculations reveal that Ni3N is the intrinsic active component for the hydrogenolysis, which exhibits efficient activity for the dissociation of C‒O bond. This work opens up a new avenue to develop catalysts with single non-noble metal component for the efficient conversion of biomass-based chemicals.

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Clarifying sequential electron-transfer steps in single-nanoparticle electrochemical process for identifying the intrinsic activity of electrocatalyst Zehui Sun, Zhuangzhuang Lai, Yingying Zhao, Jianfu Chen, Wei Ma 2024, 60:  262-271.  DOI: 10.1016/S1872-2067(24)60015-X Abstract ( 220 )   HTML ( 9 )   PDF (2314KB) ( 67 )   Supporting Information Single-nanoparticle collision electrochemistry (SNCE) is an effective method for determining the intrinsic activity of electrocatalysts at the single-nanoparticle (NP) level. Despite fruitful advancements in the SNCE field, determining a quantitative relationship between the NP structure and its activity has remained difficult because of an unclear understanding of SNCE. In this study, we successfully uncovered the essential roles of the sequential electron-transfer steps in the SNCE system in regulating the apparent electrocatalytic activity of single NPs. By monitoring the oxygen reduction reaction of individual Pt NPs, significantly distinct apparent activities were observed at different electrodes owing to the rate-determining step-controlled electron transfer process. Furthermore, a new theoretical model is proposed for treating the electrochemical current, which involves NP-electrode electron transfer, heterogeneous electron transfer, and mass transfer in solution as sequential steps in the SNCE system. The combination of theoretical simulations and high-resolution electrochemical measurements allows for the corresponding parameters (contact resistance, heterogeneous kinetic constants, and adsorption possibility) of sequential electron-transfer steps to be quantified, resulting in the identification of a rate-determining step for improving the intrinsic activity of electrocatalysts. This work provides a clear picture for determining the intrinsic activity of single NPs in SNCE measurements and introduces a new conceptual route for the quantification of structure-activity relationships, which ultimately guide the rational design and optimization of electrocatalytic nanomaterials.

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Engineering fully exposed edge-plane sites on carbon-based electrodes for efficient water oxidation Jingya Guo, Wei Liu, Wenzhe Shang, Duanhui Si, Chao Zhu, Jinwen Hu, Cuncun Xin, Xusheng Cheng, Songlin Zhang, Suchan Song, Xiuyun Wang, Yantao Shi 2024, 60:  272-283.  DOI: 10.1016/S1872-2067(24)60018-5 Abstract ( 130 )   HTML ( 3 )   PDF (6359KB) ( 45 )   Supporting Information Endowing metal-free graphitic carbon electrodes with high electrocatalytic reactivity is a field of intense research, but remains elusive. Here, we introduce a prototypical edge-plane-site-specific engineering strategy on “herringbone” multi-walled carbon nanotubes by performing an intercalation-exfoliation and truncation process in molten inorganic salts. Controllable synthesis of the target H-MWCNTs-MS with fully exposed edge-plane sites on both the outer surface and inner channels was demonstrated. in-situ infrared spectroscopic study supports the theoretically energetic “edge-state” and identifies the reconstructed ketone/carboxyl-terminated edge sites under oxygen evolution reaction (OER) conditions. These oxygenated edge-plane sites boost charge redistribution and interlayer coupling, which essentially govern the synergistic catalysis, as evidenced by combined theoretical, electrokinetic, and H/D isotopic studies. Benefiting from the dense reactive sites and efficient electron tunneling, the H-MWCNTs-MS demonstrated impressive OER activity with an overpotential of 236 mV at a current density of 10 mA cm‒2 in alkaline media, outperforming most state-of-the-art metal-free electrocatalysts reported to date. Furthermore, the catalyst displayed no noticeable degradation during 100 h of operation, indicating its potential for practical applications.

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On the temperature dependence of enzymatic degradation of poly(ethylene terephthalate) Ekram Akram, Yufei Cao, Hao Xing, Yujing Ding, Yuzheng Luo, Ren Wei, Yifei Zhang 2024, 60:  284-293.  DOI: 10.1016/S1872-2067(23)64628-5 Abstract ( 343 )   HTML ( 9 )   PDF (2439KB) ( 73 )   Supporting Information Enzymatic recycling of poly(ethylene terephthalate), PET, has attracted significant attention in recent years. Temperature is a governing factor in the enzymatic degradation of PET, influencing simultaneously the catalytic activity and thermal stability of enzymes, as well as the biodegradability of PET materials from many perspectives. Here we present a detailed examination of the complex and mutual effects of temperature on the degradation of low-crystallinity PET (LC-PET, 7.6%) and high-crystallinity PET (HC-PET, 30%) microparticles using the WCCG variant of the leaf-branch compost cutinase (LCC). The degradation velocity apparently increases exponentially with increasing temperature at temperatures below 65 °C. Arrhenius plots show a sudden reduction in activation energy at temperatures higher than 40 °C, suggesting the onset of the surface glass transition of PET particles. This is more than 20 °C lower than the bulk glass transition temperature, underscoring the interfacial catalytic nature of enzymatic PET degradation. WCCG undergoes substantial conformational changes upon thermal incubation at temperatures ranging from 50 to 70 °C and exhibits enhanced activity, owing to the increased intrinsic catalytic activity and improved adsorption on PET surface. Further increasing the temperature leads to the inactivation of enzymes alongside the rapid recrystallization of amorphous PET, impeding the enzymatic degradation. These findings offer a detailed mechanistic understanding of the temperature dependence of the enzymatic degradation of PET, and may have implications for the engineering of more powerful PET hydrolases and the selection of favorable conditions for industrially-related recycling processes.

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Light-driven CO2 utilization for chemical production in bacterium biohybrids Yamei Gan, Tiantian Chai, Jian Zhang, Cong Gao, Wei Song, Jing Wu, Liming Liu, Xiulai Chen 2024, 60:  294-303.  DOI: 10.1016/S1872-2067(23)64643-1 Abstract ( 174 )   HTML ( 8 )   PDF (3032KB) ( 59 )   Supporting Information Artificial photosynthetic systems provide an alternative approach for the sustainable, efficient, and versatile production of biofuels and biochemicals. However, improving the efficiency of electron transfer between semiconductor materials and microbial cells remains a challenge. In this study, an inorganic-biological photosynthetic biohybrid system (IBPHS) consisting of photocatalytic and biocatalytic modules was developed by integrating cadmium telluride quantum dots (CdTe QDs) with Escherichia coli cells. A photocatalytic module was constructed by biosynthesizing CdTe QDs to capture light and generate electrons. The biocatalytic module was built by converting photo-induced electrons to enhance NADH regeneration; thus, the NADH content in E. coli under blue light increased by 5.1-fold compared to that in darkness. Finally, IBPHS was utilized to drive CO2 reduction pathways for versatile bioproduction such as formate and pyruvate, with CO2 utilization rates up to 51.98 and 21.92 mg/gDCW/h, respectively, exceeding that of cyanobacteria. This study offers a promising platform for the rational design of biohybrids for efficient biomanufacturing processes with high complexity and functionality.

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Design of earth-abundant Ni3ZnC0.7@Ni@C catalyst for selective butadiene hydrogenation Zhibing Chen, Xintai Chen, Yali Lv, Xiaoling Mou, Jiahui Fan, Jingwei Li, Li Yan, Ronghe Lin, Yunjie Ding 2024, 60:  304-315.  DOI: 10.1016/S1872-2067(23)64641-8 Abstract ( 214 )   HTML ( 1 )   PDF (12058KB) ( 85 )   Supporting Information The pursuit of developing catalysts from earth-abundant materials to supplant those based on precious metals is of paramount importance in selective hydrogenations. While nickel-based systems have shown promise in the selective hydrogenation of butadiene, their practical applications are hampered by severe deactivation issues due to coke deposition and excessive hydrogenation. Here, a novel catalyst, Ni3ZnC0.7@Ni@C, is ingeniously engineered through the controlled oxidation of Ni3ZnC0.7@C. This catalyst is characterized by small Ni0 ensembles elegantly embellishing the Ni3ZnC0.7 nanoparticles, all encased within porous carbon shells. The evolutions of this catalyst, in terms of composition and structure during the oxidation process, is meticulously observed and characterized using a spectrum of advanced techniques. The Ni3ZnC0.7@Ni@C catalyst exhibits outstanding activity and stability in the hydrogenation of butadiene, surpassing other Ni-based systems, including its precursor Ni3ZnC0.7@C and other previously documented catalysts such as Ni3InC0.5 and the Ni3In alloy. A pivotal finding of this research is the self-limiting behavior of coke deposition in the initial reaction stages. This intriguing phenomenon not only curbs further deactivation but also significantly enhances butene production, maintaining operational stability for an impressive duration of 80 hours. This discovery underscores the advantageous role of in situ generated 'soft' cokes in augmenting the selectivity and stability of the catalyst, which is particularly enlightening for other catalytic processes that are similarly afflicted by coking issues, thereby opening avenues for further in-depth investigations in this field.

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PS-PPh2 tethered Pt single atoms promoted by SnCl2 as highly efficient and regio-selective catalysts for the hydroformylation of higher α-alkenes Zhounan Yu, Leilei Zhang, Yuanlong Tan, Rizheng Jing, Hongchen Cao, Caiyi Lou, Rile Ge, Junhu Wang, Aiqin Wang, Tao Zhang 2024, 60:  316-326.  DOI: 10.1016/S1872-2067(24)60029-X Abstract ( 147 )   HTML ( 7 )   PDF (4779KB) ( 64 )   Supporting Information Rh-P complexes have been widely used as catalysts for hydroformylation reactions. The extremely high price of Rh and its scarce reserves have prompted the exploration of the alternatives. In this study, we reported that Pt/PS-PPh2 single-atom catalysts promoted by SnCl2 were highly efficient and selective for the hydroformylation of higher α-alkenes. A broad scope of substrates (i.e., C6‒C12) were smoothly converted to the corresponding linear aldehydes with high yields under reaction conditions of 90‒120 °C and 4‒6 MPa syngas. The turnover frequency (TOF) was comparable to homogeneous Pt-Sn catalysts, and the linear/branched ratio reached as high as > 20. In addition, the catalyst could be reused with the extra addition of SnCl2. The promotional role of SnCl2 was elucidated by quasi-in situ X-ray adsorption fine structure, Fourier transform infrared, and Mössbauer spectroscopy. It was discovered that SnCl2 was transformed into Sn(dioxane)Cl3‒ species coordinated to Pt as a moderately electron-donating ligand, which, together with the phosphine group, stabilized mononuclear Pt (I) species against reduction and aggregation.

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Mo-promoted Pd/NaY catalyst for indirect oxidative carbonylation of methanol to dimethyl carbonate Ke Huang, Shicheng Yuan, Rongyan Mei, Ge Yang, Peng Bai, Hailing Guo, Chunzheng Wang, Svetlana Mintova 2024, 60:  327-336.  DOI: 10.1016/S1872-2067(24)60019-7 Abstract ( 167 )   HTML ( 5 )   PDF (5133KB) ( 60 )   Supporting Information A chlorine-free catalyst consisting of zeolite Y modified with Pd (Pd/NaY) catalyst has been prepared and used in the indirect oxidative carbonylation of methanol to dimethyl carbonate (DMC). The activity and stability of the catalyst were further improved by introducing molybdenum into Pd/NaY using a top-down approach (Pd-Mo/NaY catalyst). The Pd-Mo/NaY catalyst exhibited higher stability compared to the Pd/NaY. A high CO conversion of 97% and DMC selectivity of 80% during a 30-hour catalytic test for the Pd-Mo/NaY were obtained. Furthermore, the incorporation of Mo was found to partially heal the silanols and hinder the aggregation of Pd in the Pd-Mo/NaY catalyst. The interactions between Mo and Pd increased the amount of active Pd2+ species and enhanced the adsorption of CO reactant on the Pd-Mo/NaY catalyst. The key reaction intermediate of COOCH3* was captured by in situ diffuse reflectance infrared Fourier transform spectroscopy. The stabilization of active Pd2+ species contributed to the enhanced catalytic activity of the Pd-Mo/NaY catalyst in the indirect oxidative carbonylation of methanol to DMC reaction.

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Alkali-modified copper manganite spinel for room temperature catalytic oxidation of formaldehyde in air Yongbiao Hua, Kumar Vikrant, Ki-Hyun Kim, Philippe M. Heynderickx, Danil W. Boukhvalov 2024, 60:  337-350.  DOI: 10.1016/S1872-2067(24)60022-7 Abstract ( 166 )   HTML ( 10 )   PDF (5342KB) ( 55 )   Supporting Information Formaldehyde (FA) is present ubiquitously in indoor environment as a hazardous pollutant with carcinogenic risks. For the efficient mitigation of FA, catalytic oxidation is a recommendable option to simultaneously satisfy both material cost (e.g., avoiding noble metals) and low-energy requirement (under dark and at room temperature (RT)). From this perspective, a cost-effective alkali modified copper manganite spinel (CuMn2O4) catalyst has firstly been prepared and employed for FA oxidation. Specifically, alkali (1 mol L−1 potassium hydroxide)-modified CuMn2O4 (1-CuMn2O4) achieves 100% FA (50 ppm (gas hourly space velocity of 4777 h−1)) conversion (XFA) at RT. The steady-state reaction rate of 1-CuMn2O4 at 10% XFA is 8.18 × 10‒2 mmol g−1 h−1. According to in situ diffuse reflectance infrared Fourier transform spectroscopy, FA molecules are oxidized into water and carbon dioxide through dioxymethylene and formate intermediates. Based on density functional theory simulation, the higher catalytic performance of 1-CuMn2O4 for FA oxidation is attributed to the combined effects of firmer attachment of FA molecules to 1-CuMn2O4 surface, lower energy cost of FA adsorption, and lower desorption energy for the final products from the substrate surface. The present work is expected to provide insights into high-performing non-noble metal catalysts for RT oxidative removal of FA from indoor air.

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Amorphization of MOFs with rich active sites and high electronic conductivity for hydrazine oxidation Jieting Ding, Hao-Fan Wang, Kui Shen, Xiaoming Wei, Liyu Chen, Yingwei Li 2024, 60:  351-359.  DOI: 10.1016/S1872-2067(24)60035-5 Abstract ( 274 )   HTML ( 8 )   PDF (4033KB) ( 75 )   Supporting Information The applications of metal-organic frameworks (MOFs) in electrocatalysis are limited by the perfect crystalline nature with insufficient coordinatively unsaturated sites and low electronic conductivity. Here, we report an electrosynthesis method to induce rapid assembly of amorphous MOFs on carbon cloth (denoted as aMnFc'/CC), achieving the amorphization of MOFs with rich active sites and high electronic conductivity. The long-range disordered structure of aMnFc'/CC forms a large number of oxygen vacancies to modify the coordination and electronic structures of Mn sites. In the electrocatalytic hydrazine oxidation reaction (HzOR), the aMnFc'/CC electrocatalyst exhibits superior activity to its crystalline MOF counterparts. Density functional theory calculations reveal that the unsaturated Mn centers present in aMnFc'/CC facilitate efficient electron transfer while simultaneously lowering the free energy of the rate-determining step in the HzOR process.

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Ultralow Ru-doped NiMoO4@Ni3(PO4)2 core-shell nanostructures for improved overall water splitting Adel Al-Salihy, Ce Liang, Abdulwahab Salah, Abdel-Basit Al-Odayni, Ziang Lu, Mengxin Chen, Qianqian Liu, Ping Xu 2024, 60:  360-375.  DOI: 10.1016/S1872-2067(24)60038-0 Abstract ( 162 )   HTML ( 13 )   PDF (6904KB) ( 66 )   Supporting Information The potential of sustainable hydrogen production technology through water splitting necessitates the rational design of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) bi-functional electrocatalysts. In this context, we initially synthesized and empirically evaluated ultralow Ru-doped NiMoO4@Ni3(PO4)2 core-shell nanostructures on nickel foam (Ru-NiMoO4@Ni3(PO4)2/NF). The hydrous NiMoO4 nanopillars were hydrothermally grown on NF, followed by successive RuCl3 etching and subsequent phosphorylation processes, leading to the final Ru-NiMoO4@Ni3(PO4)2/NF. The catalyst demonstrated impressive HER overpotential values of −14.8 and −57.1 mV at 10 and 100 mA cm-2, respectively, with a Tafel slope of 35.8 mV dec-1. For OER at 100 mA cm-2, an overpotential of 259.7 mV was observed, with a Tafel slope of 21.6 mV dec-1. The cell voltage required for overall water splitting was 1.43 V at 10 mA cm-2 and 1.68 V at 100 mA cm-2. Moreover, the catalyst exhibited superior stability for 150 h, emphasizing its practical utility for long-term applications. Subsequent density functional theory calculations aligned with these empirical findings, indicating a low water dissociation energy barrier (ΔGb = 0.46 eV), near-zero free adsorption energy for HER (∆G*H = 0.02 eV), and suitable free adsorption energy for OER (ΔG*OOH − ΔG*OH = 2.74 eV), alongside a high density of states near the Fermi level. These results, informed by both experimental evaluation and theoretical validation, highlight the potential of Ru-NiMoO4@Ni3(PO4)2/NF as a high-performance catalyst for water splitting, setting a solid foundation for advancements in sustainable energy technologies.

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Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid Jie Wang, Yihe Chen, Yuda Wang, Hao Zhao, Jinyu Ye, Qingqing Cheng, Hui Yang 2024, 60:  376-385.  DOI: 10.1016/S1872-2067(24)60024-0 Abstract ( 236 )   HTML ( 12 )   PDF (6687KB) ( 76 )   Supporting Information Electrochemical oxidation of ethylene is a novel approach to manufacture valuable ethylene glycol (EG), which is an important raw material in organic chemical industry. However, the poor EG selectivity and expensive additional purification costs hinder this method from being practically used. In this work, ultrafine iridium-ruthenium (IrRu) alloy nanoparticles are synthesized through the precipitation-reduction method and their electrocatalytic performance towards ethylene oxidation to EG has been comprehensively studied. Near 100% selectivity is achieved with a EG yield of 60.62 mmol gRu-1 h-1 at 1.475 V on an optimal Ir0.54Ru0.46 catalyst. OH-stripping, in-situ electrochemical attenuated total internal reflectance Fourier transform infrared spectra and DFT calculation reveal that the introduction of Ir can modulate the electronic structure and d-band center so as to endow the Ru with the mild binding energy with the key intermediates and small energy barrier for *HOCH2CH2OH desorption, thereby enhancing the EG generation. Simultaneously, the high energy barrier for the overoxidation of the *CH2CH2OH renders the EG formation thermodynamically favorable, thus realizing the near 100% EG selectivity. This work provides a new understanding for the high-selectivity electrosynthesis of high-value-added oxides.

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Multivariate mesoporous MOFs with regulatable hydrophilic/hydrophobic surfaces as a versatile platform for enzyme immobilization Yuxiao Feng, Qingqing Ma, Zichen Wang, Qunli Zhang, Lixue Zhao, Jiandong Cui, Yingjie Du, Shiru Jia 2024, 60:  386-398.  DOI: 10.1016/S1872-2067(24)60020-3 Abstract ( 361 )   HTML ( 14 )   PDF (3717KB) ( 120 )   Supporting Information Zeolitic imidazole frameworks materials-8 (ZIF-8), a member of the metal-organic framework (MOFs) series, have been extensively used as a host matrix for enzyme immobilization. However, the microporous structure and hydrophobicity, as well as the protonation of the precursor 2-methylimidazole (2-MeIm) of ZIF-8, remain considerable challenges in maintaining the activity of immobilized enzymes. Here, novel multivariate mesoporous MOFs (mMOFs) with regulatable hydrophilic/hydrophobic surfaces were designed by the multivariate competitive strategy and pore modification engineering. 3-Methyl-1H-1,2,4-triazole (3-MTZ) and 5-methyltetrazole (5-MTA) were employed to partially replace 2-MeIm. These were then combined with zinc sulfate heptahydrate (soft templates) to yield mMOFs in a methanol solution. As a proof-of-concept application, we used mMOFs as carriers for enzyme immobilization and investigated the properties of the immobilized enzymes. Benefiting from their mesoporous structure, hydrophilic surface, and improved microenvironment, multivariate mMOFs exhibit a strong ability to stabilize enzyme conformation and increase enzyme activity compared with traditional ZIF-8. Our study offers an avenue for the controllable preparation of well-designed MOF structures, which will further broaden the application opportunities of MOF materials for enzyme immobilization.