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Chinese Journal of Catalysis
2024, Vol. 58
Online: 18 March 2024

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Cover: Professor Wee-Jun Ong and coworkers reported the synthesis and modification strategies for creating porous electrocatalysts tailored for electrocatalytic hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and overall water splitting (OWS). The study delves deeply into the latest developments in terms of the recent advancements in the synthesis strategies and diverse modification approaches, highlighting the distinctive contributions of porous structures. This review serves as a valuable guide for designing and modifying the porous-based materials with distinct properties, paving the way for the production of highly efficient electrocatalysts for electrocatalytic water splitting. Read more about the article behind the cover on page 37–85.

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Electrochemical synthesis in company with hydrogen production via renewable energy: Opportunities and challenges Zidong Wei, Xun Huang, Haohong Duan, Mingfei Shao, Rengui Li, Jinli Zhang, Can Li, Xue Duan 2024, 58:  1-6.  DOI: 10.1016/S1872-2067(23)64625-X Abstract ( 110 )   HTML ( 21 )   PDF (2257KB) ( 120 )   Organic electromechanical synthesis is an eco-friendly and efficient method for material synthesis, effectively addressing the high energy consumption and pollution problems in the traditional chemical industry. By combining hydrogen production from water electrolysis with organic electromechanical synthesis, the reactive oxygen/hydrogen from water hydrolysis can be utilized to oxidize/reduce organic compounds, reducing energy consumption and producing valuable organic products. However, this strategy still faces challenges when implemented in the industry. This paper addresses major technical challenges in the field, providing new insights for future advancements. Firstly, when selecting anode reactions for hydrogen production, it is important to consider the value and market demand of the oxidation product to match the production scale. Secondly, the development of efficient electrocatalysts and electrodes is required to enhance the oxidation kinetics and mass transfer of organics at the current density levels of industrial hydrogen production (500‒2000 mA cm‒2). Thirdly, it is essential to improve the selectivity and Faraday efficiency of the anode target product to lower the cost of subsequent separation and purification. Fourthly, existing anion and oxygen ion exchange membranes lack corrosion resistance to organic matter, and new separator materials with high ion conductivity and stability are crucial for the electrolytic coupling system. Finally, when combining organic oxidation and water electrolysis, the complexity of product separation increases, and it is recommended to integrate distillation, extraction, membrane separation, and electrochemical reactions to improve process efficiency.

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Synergy between heterogeneous catalysis and homogeneous radical reactions for pharmaceutical waste destruction: Perspective Dmitry Yu. Murzin 2024, 58:  7-14.  DOI: 10.1016/S1872-2067(23)64599-1 Abstract ( 65 )   HTML ( 8 )   PDF (1295KB) ( 46 )   Enormous quantities of pharmaceuticals are consumed by humans leading to a growing and continuous release of harmful components into the environment. Existing conventional water treatment plants are designed mainly for eliminating biodegradable organics and nutrients and cannot degrade pharmaceuticals and personal care products efficiently enough due to their chemical stability. Advanced oxidation processes using radicals generated from ozone can be efficiently combined with heterogeneous catalysis for treatment of wastewater containing pharmaceuticals and personal care products. From the technology viewpoint, elimination of pharmaceuticals from water by heterogeneously catalyzed ozonation should done in a continuous fixed bed reactor. The structured catalysts can be prepared by additive manufacturing using 3D-direct printing of supports/catalysts allowing a high degree of freedom in both the composition and design of the final catalytic material for a fixed bed heterogeneous-homogeneous reaction. Structured materials can exhibit non-periodic structure, such as for example semi-ordered structures, inspired by nature. For periodic and semi-periodic structures, heat and mass transfer should be investigated using computational fluid dynamics and flow imaging methods, guiding further design of novel architectures and subsequently allowing in combination with the materials development efficient control of activity and selectivity. The innovative catalytic reactor engineering should include experimental and numerical investigation of the stage wise injection of the oxidation agent, variation of the reactor cross-section size, changing the distance between the catalyst beds and introduction of the recycle loops.

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Catalytic conversion of triglycerides into diesel, jet fuel, and lube base oil Yaejun Baik, Kyeongjin Lee, Minkee Choi 2024, 58:  15-24.  DOI: 10.1016/S1872-2067(23)64617-0 Abstract ( 50 )   HTML ( 9 )   PDF (2029KB) ( 53 )   The conversion of biomass into sustainable fuels and chemicals is essential for addressing environmental concerns, reducing the carbon footprint of the energy sector, enhancing energy security, and promoting economic and social development. Among various biomass feedstocks, triglycerides from diverse sources, such as vegetable oils, animal fats, and microalgal oils, are particularly suitable for producing sustainable hydrocarbon fuels and chemicals due to their low oxygen contents and highly paraffinic backbone in the fatty acid units, the structures of which are already quite similar to those of petroleum-derived hydrocarbons. This implies that relatively simple catalytic conversions can effectively convert triglycerides into hydrocarbon products. In this Perspective, we will provide an overview on the hydroconversion of triglycerides into oxygen-free fuels, such as diesel and jet fuel, and value-added products such as lube base oil. In addition, we will discuss the important structural properties of the required catalysts and the effects of different fatty acid compositions of triglycerides for each conversion process in light of reaction mechanisms.

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Electrocatalytic nitrate reduction to ammonia: A perspective on Fe/Cu-containing catalysts Lili Chen, Yanheng Hao, Jianyi Chu, Song Liu, Fenghua Bai, Wenhao Luo 2024, 58:  25-36.  DOI: 10.1016/S1872-2067(23)64605-4 Abstract ( 100 )   HTML ( 14 )   PDF (3695KB) ( 54 )   Electrocatalytic reduction reaction of nitrate (NO3RR) to ammonia is becoming ever more pivotal for the sustainable production of NH3, alleviating the nitrate pollution and even for rebalancing the nitrogen cycle globally. Considerable efforts have been devoted to the rational development of catalyst systems in electrocatalytic NO3RR to NH3, and Fe/Cu-containing catalysts have shown significant advantages and are currently in the spotlight which have addressed remarkable attention and academic interest. In this Perspective, we first briefly discuss the possible reaction pathways of electrocatalytic NO3RR to NH3. Emphasis is put on the three catalyst approaches for enhancing the NO3RR performance, based on the selected case studies of the most representative Fe/Cu-containing catalysts. Furthermore, this Perspective assesses the recent progress on the utility and application of the state-of-the-art in situ characterization technologies applied in recent showcases of electrocatalytic NO3RR to NH3, with a special focus on spectroscopies. Finally, the open challenges and outlook regarding the rational design of efficient electrocatalysts, the development of correlative in situ characterization technologies and the further coupling promising reactions for production of value-added products are examined for inspiring the future work.

Review

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Unleashing the versatility of porous nanoarchitectures: A voyage for sustainable electrocatalytic water splitting Jian Yiing Loh, Joel Jie Foo, Feng Ming Yap, Hanfeng Liang, Wee-Jun Ong 2024, 58:  37-85.  DOI: 10.1016/S1872-2067(23)64581-4 Abstract ( 82 )   HTML ( 16 )   PDF (40545KB) ( 45 )   Electrochemical overall water splitting (OWS) has drawn much research fascination as a promising technology for energy conversion to produce clean hydrogen fuel as sustainable chemical resources. However, half reaction of the water splitting reaction, which is oxygen evolution reaction (OER) is the main challenge due to the sluggish kinetics and large thermodynamic barrier. Porous-based materials can markedly enhance the accessibility of active sites, increase specific surface area and optimize the adsorption/desorption of reactants. The enhanced activity arising from the porous materials is attributed to the increase in active sites and improved mass transfer. Herein, the recent research advances made in porous electrocatalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and OWS are reviewed. This review focuses on the recent advancements in the synthesis strategies, incorporated with the unique roles of porous structure in electrocatalysts are discussed. For boosting the activity, various emerging modification strategies on porous electrocatalysts, covering structure engineering, phase engineering, defect engineering and strain engineering are presented. This review emphasizes on the synthesis methods, how porous materials improve the performance, mechanistic understanding, integrated experiments, theoretical studies in water splitting, advanced modification strategies and proposed synthesis processes. Specially, the structural-activity relationship gives insights into designing and modifying the porous-based materials with unique properties. Finally, the current science challenges and direction for the future development of porous electrocatalysts are highlighted.

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Progress on facet engineering of catalysts for application in photo/electro-catalysis Qi Li, Jiehao Li, Huimin Bai, Fatang Li 2024, 58:  86-104.  DOI: 10.1016/S1872-2067(23)64600-5 Abstract ( 72 )   HTML ( 15 )   PDF (7969KB) ( 55 )   The conversion and storage of solar or electrical energy into chemical energy through photo/electro-catalysis technology shows fascinating potential for alleviating the energy crisis. The application of facet engineering in photo/electrocatalytic materials has shown significant advantages, making it an attractive and challenging topic at the intersection of physics and chemistry. In recent years, from basic scientific research to practical applications, facet engineering has made significant progress in photo/electro-catalytic reactions. In this review, we mainly focus on the microscopic mechanisms of facet engineering and how it specifically affects photo/electro-catalytic reactions, including CO2 reduction, hydrogen evolution, and nitrogen reduction. The microscopic mechanisms are elucidated and direct evidence for improving catalytic reactions is revealed through advanced spectroscopic characterization and theoretical analysis. Based on the microscopic mechanisms of facet engineering, the design principles and breakthrough directions for facet engineering are proposed, such as LSPR and single atom modification etc. In particular, we emphasize the controllable preparation methods for facet exposure from the aspects of capping agents, pH regulation and precursor hydrolysis, etc. Finally, the outlooks and future development prospects of facet engineering are briefly discussed.

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Near infrared-driven photocatalytic overall water splitting: Progress and perspective Yuanyong Huang, Hong Yang, Xinyu Lu, Min Chen, Weidong Shi 2024, 58:  105-122.  DOI: 10.1016/S1872-2067(23)64594-2 Abstract ( 45 )   HTML ( 7 )   PDF (7406KB) ( 27 )   The conversion of solar energy into clean and sustainable hydrogen (H2) fuel from water using simple and cost-effective photocatalytic technologies is one of the most potential ways for achieving carbon neutrality. However, the near-infrared (NIR) region of solar spectrum, which encompasses approximately half of the total solar photon flux, remains an abundant energy source that is currently underutilized. The exploration of NIR-active photocatalysts for solar overall water splitting, as highlighted here, represents not only a momentous breakthrough towards sustainable H2 generation, but also initiates a new chapter in the realm of artificial photosynthesis. In this review, we delve into the latest advancements in material design and engineering of NIR-active and full-spectrum-responsive photocatalysts for solar overall water splitting, highlighting their current status and potential impact. A primary focus is on gaining a fundamental understanding of the intricate relationship between material characteristics, catalytic properties, and functional mechanisms underlying the NIR-driven water splitting process. Furthermore, we outline the challenges and future prospects for further exploiting the vast potential of NIR-activated photocatalysts in solar overall water splitting.

Communication

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Chlorine radical-mediated photocatalytic C(sp3)-H bond oxidation of aryl ethers to esters Yuting Liu, Beili Nie, Ning Li, Huifang Liu, Feng Wang 2024, 58:  123-128.  DOI: 10.1016/S1872-2067(23)64615-7 Abstract ( 61 )   HTML ( 25 )   PDF (1961KB) ( 45 )   Supporting Information The C(sp3)-H functionalization of naturally abundant alkanes is of great importance, whereas C-H bond oxidation of aryl ethers in a redox-neutral and environmental-friendly manner remains a challenge. Herein, we report a novel method of visible-light-driven C(sp3)-H bond oxidation of aryl ethers selectively into ester products using oxygen as the oxidant. During the photocatalytic reaction using Mes-10-phenyl-Acr+-BF4- catalyst, chlorine radicals are generated from a wide variety of chloride sources and can effectively activate aryl ether C(sp3)-H bonds into alkyl radicals through the hydrogen atom transfer process. Aryl ethers with different substituents can be oxidized to esters in good to excellent yields. This work presents a new photocatalytic strategy for C(sp3)-H oxidation of aryl ethers in a convenient and green manner.

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Mutualism in organic synthetic chemistry: Simultaneous heterodehydrocoupling of hydrostannane and reduction of quinoline Tianwei Liu, Jianghua He, Yuetao Zhang 2024, 58:  129-137.  DOI: 10.1016/S1872-2067(23)64590-5 Abstract ( 171 )   HTML ( 11 )   PDF (1430KB) ( 38 )   Supporting Information Here we report a one-pot strategy to simultaneously achieve both the heterodehydrocoupling of hydrostannane and reduction of quinoline by using B(C6F5)3 as catalyst under mild conditions. This method realizes the synthesis of heteroatom-tin complexes (NSn/OSn/PSn/SSn) by the same catalyst system. With the assistance of quinoline, the substrate scope was broadened and ESn yield was significantly enhanced. During the reaction, the generated heterodehydrocoupling intermediate [ESnH]+[HB(C6F5)3]- would accelerate the quinoline reduction by transforming 1,4-N-stannyl-dihydroquinoline intermediate into N-stannyl-tetrahydroquinoline whereas 1,4-N-stannyl-dihydroquinoline could serve as hydrogen acceptor to facilitate the conversion of [ESnH]+[HB(C6F5)3]- intermediate to produce ESn (E = N/O/P/S). The metathetical reaction of N-stannyl-tetrahydroquinoline and EH rapidly generates ESn and tetrahydroquinolines, thus mutually promoting the above process. The reaction mechanism is proposed on the basis of control experiments, capture and synthesis of key intermediates and deuterium experiments.

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Functional ladder-like heterojunctions of Mo2C layers inside carbon sheaths for efficient CO2 fixation Yu-Shuai Xu, Hong-Hui Wang, Qi-Yuan Li, Shi-Nan Zhang, Si-Yuan Xia, Dong Xu, Wei-Wei Lei, Jie-Sheng Chen, Xin-Hao Li 2024, 58:  138-145.  DOI: 10.1016/S1872-2067(23)64595-4 Abstract ( 31 )   HTML ( 2 )   PDF (2059KB) ( 12 )   Supporting Information The development of two-dimensional heterogeneous catalysts with highly exposed active site areas for heterogeneous catalytic systems is highly promising for achieving the green transformation of small molecules. 2D transition metal carbides (TMCs) show great promise for catalysis and carbon capture but suffer from heavy aggregation and autooxidation. Mass transfer barrier is also a standard problem of lamellar TMCs caused by slight aggregation of layers. Here, we successfully developed a method to prepare “ladder-like” heterojunctions of Mo2C layers confined inside nitrogen-rich carbon sheaths (2D-Mo2C@NC) via an effective oxygen-diffusion etching strategy, acting as efficient catalysts for CO2 fixation. The enhanced electron enrichment of the as-integrated 2D-Mo2C subunits induced by the Schottky barrier could further keep the exposed Mo2C surface from possible autooxidation and aggregation confronted by conventional 2D TMCs. The experimental results and density functional theory (DFT) calculation further demonstrate that electron-rich Mo2C could boost the adsorption and activation of CO2 for universal carbonylation of various diamines, providing a turnover frequency value (TOF) of 10.2 h-1 to produce benzimidazolone, which is 5.2 times of that of the state-of-the-art catalyst in the literature under even critical conditions.

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Electronic modification of Ni active sites by W for selective benzylamine oxidation and concurrent hydrogen production Zhentao Tu, Xiaoyang He, Xuan Liu, Dengke Xiong, Juan Zuo, Deli Wu, Jianying Wang, Zuofeng Chen 2024, 58:  146-156.  DOI: 10.1016/S1872-2067(23)64596-6 Abstract ( 70 )   HTML ( 3 )   PDF (20260KB) ( 41 )   Supporting Information We present self-supporting W-doped Ni2P nanosheet arrays, serving as bifunctional catalysts for selective electrooxidation of benzylamine (BA) to high-value benzonitrile (BN), while simultaneously promoting hydrogen production. The assembled W-Ni2P/NF||W-Ni2P/NF (NF: nickel foam) electrolyzer requires a voltage of only 1.41 V to achieve a current density of 10 mA cm‒2 in alkaline solution containing 25 mmol L‒1 BA, exhibiting an impressive Faradaic efficiency 95% for benzonitrile synthesis. In-situ Raman and FTIR spectroscopies identify catalytically active NiOOH centers and key catalytic intermediates. X-ray absorption spectroscopy (XAS) and theoretical calculations suggest that W acts as electron attractors on adjacent Ni atoms, forming an electron-deficient Ni domain that promotes the adsorption and activation of -NH2 group, leading to efficient dehydrogenation into C≡N bonds. The doped W also optimizes the adsorption of hydrogen (ΔGH*) on Ni2P, thus promote the hydrogen evolution. This work highlights the electronic modification of Ni active sites as a key factor for bifunctional electrocatalysis in selective nitrile electrosynthesis and concurrent hydrogen evolution.

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Ipolymer Cd3(C3N3S3)2/Zn3(C3N3S3)2 S-scheme heterojunction enhances photocatalytic H2 production Tingting Yang, Jing Wang, Zhongliao Wang, Jinfeng Zhang, Kai Dai 2024, 58:  157-167.  DOI: 10.1016/S1872-2067(23)64607-8 Abstract ( 29 )   HTML ( 4 )   PDF (4479KB) ( 29 )   The preparation of S-scheme heterojunctions has attracted considerable attention in the academic community as a highly effective approach to enhance the separation and migration of electrons and holes, thereby significantly improving the catalytic efficiency of photocatalysts. In this work, a novel S-scheme ipolymer heterojunction photocatalyst, Cd3(C3N3S3)2/Zn3(C3N3S3)2 (CdTMT/ZnTMT), which synergy with π-conjugate system, was synthesized using an innovative in-situ hydrothermal method. Through a series of rigorous characterization tests, the formation of an S-scheme heterojunction between CdTMT and ZnTMT was confirmed. Particular emphasis is placed on the effective enhancement of photocatalytic activity of photocatalysts through π-conjugated orbitals and built-in electric field after combining double-organic conjugated polymer-shaped ZnTMT and CdTMT. Performance tests that show the photocatalytic hydrogen evolution performance of the composite was significantly boosted to an impressive 45.24 mmol∙g-1∙h-1, which is 215.43 times that of single catalyst ZnTMT and 1.76 times that of CdTMT. Finally, this paper discusses the possibility and development prospect of double polymer to construct S-scheme heterojunctions to improve the activity of photocatalysts.

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Primary alcohols as killers of Ni-based catalysts in transfer hydrogenation Nikolay Nesterov, Alexey Philippov, Vera Pakharukova, Evgeny Gerasimov, Stanislav Yakushkin, Oleg Martyanov 2024, 58:  168-179.  DOI: 10.1016/S1872-2067(23)64606-6 Abstract ( 60 )   HTML ( 7 )   PDF (5479KB) ( 25 )   Supporting Information The effect of different types of alcohols used as hydrogen donors on the activity of a metal Ni-based catalyst in the hydrogenation of benzofuran as a model substrate under transfer hydrogenation conditions has been studied. The hydrogenation process of benzofuran using 2-PrOH as a hydrogen donor leads sequentially to dearomatization and then to deoxygenation of the substrates. At the same time, the use of primary alcohols such as MeOH, EtOH and 1-PrOH as hydrogen donors leads to irreversible deactivation of the Ni-containing catalyst. A clear mechanism of deactivation of Ni-based metal catalysts by primary alcohols has been established. The interaction of the catalyst with primary alcohols at a temperature of 250 °C leads to the formation of an inactive Ni3C carbide phase, as well as sintering and segregation of metal particles on the surface of the alumina support.

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Construction of S-scheme heterojunction from protonated D-A typed polymer and MoS2 for efficient photocatalytic H2 production Jinkang Pan, Aicaijun Zhang, Lihua Zhang, Pengyu Dong 2024, 58:  180-193.  DOI: 10.1016/S1872-2067(23)64609-1 Abstract ( 38 )   HTML ( 4 )   PDF (6137KB) ( 33 )   Supporting Information This study involves a heterojunction (denoted as PPMS) with an intimate heterointerface and S-scheme architecture, which consisted of a conjugated polymer of protonated PyDTDO-3 featuring a donor-acceptor (D-A) configuration and a 2D-layered MoS2. The optimal PPMS-0.5% heterojunction exhibits a remarkable efficiency of 75.4 mmol g‒1 h-1 in generating H2 when subjected to visible light illumination, representing an approximately 4.6 times enhancement compared to pure PyDTDO-3. To elucidate the photocatalytic mechanism, a range of characterization methods were utilized and calculations using density functional theory were carried out. The disparity in the work function between PyDTDO-3 and MoS2 results in the creation of a Fermi-level gap. Consequently, the establishment of a built-in electric field facilitates the occurrence of the electrons in MoS2 spontaneously transferring to PyDTDO-3 at the interface. The consumption of hole on the valence band of MoS2 is accelerated by the electron transfer from the lowest unoccupied molecular orbital (LUMO) of PyDTDO-3, according to a kinetic study using femtosecond transient absorption spectra (fs-TAS). Moreover, the S-scheme PPMS exhibits a lower Gibbs free energy (ΔGH*, 0.77 eV) in comparison to the individual component, indicating it facilitates the formation of the transitional state (H*) and the effective desorption of molecular hydrogen on PPMS. Both the promoting directed charge migration and the increasing active sites contribute to the boosted photocatalytic H2 evolution.

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Construction of intramolecular and interfacial built-in electric field in a donor-acceptor conjugated polymers-based S-scheme heterojunction for high photocatalytic H2 generation Lele Wang, Wenyao Cheng, Jiaxin Wang, Juan Yang, Qinqin Liu 2024, 58:  194-205.  DOI: 10.1016/S1872-2067(23)64602-9 Abstract ( 43 )   HTML ( 8 )   PDF (9666KB) ( 28 )   Supporting Information Engineering a robust built-in electric field (IEF) is favorable for boosting carrier separation and achieving high photocatalytic performance. Herein, we developed a donor-acceptor conjugated polymer-based S-scheme heterojunction, utilizing both intramolecular and interfacial IEF to enhance carrier separation and achieve superior photocatalytic performance. Specifically, the intramolecular IEF was established by introducing 1,6-dibromopyrene into carbon nitride (CN) to form 1,6-dibromopyrene grafted CN (CNPy). Concurrently, the S-scheme heterojunction was formed by coupling CNPy with CdSe nanoparticles to create an interfacial IEF. Experimental findings demonstrated that the combined effect of intramolecular and interfacial IEF within the CdSe/CNPy heterojunction significantly improved the carrier separation and retained strong redox capacity. Benefiting from these advantages, the optimized composite, 100%CdSe/CNPy-0.2, showed the highest H2 generation rate of 1.16 mmol•g-1•h-1, surpassing those of pure CNPy-0.2, CdSe and 100%CdSe/CN by 58, 2.2 and 2.32 times, respectively. This study introduces an innovative design strategy for IEF-regulated conjugated polymer-based materials, paving the way for efficient solar-to-chemical energy conversion.

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Revolutionizing Zn-Air batteries with chainmail catalysts: Ultrathin carbon-encapsulated FeNi alloys on N-doped graphene for enhanced oxygen electrocatalysis Yibo Guo, Yuanyuan Xue, Zhen Zhou 2024, 58:  206-215.  DOI: 10.1016/S1872-2067(23)64603-0 Abstract ( 121 )   HTML ( 5 )   PDF (3158KB) ( 50 )   Supporting Information The sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) pose significant challenges for the viability of rechargeable Zn-air batteries. Developing efficient, cost-effective, stable, and dual-purpose oxygen electrocatalysts remains a formidable hurdle. In this study, we successfully synthesized a highly promising chainmail catalyst named FeNi@NC, comprising ultrathin carbon shells encapsulating FeNi alloy nanoparticles on N-doped graphene-like nanosheets. The strong synergistic effects between FeNi alloys and N-doped carbon shells result in outstanding bifunctional catalytic activity, particularly in alkaline media. Consequently, Zn-air batteries incorporating FeNi@NC as the catalyst demonstrate exceptional performance, operating reliably at high power density with extended lifespan. Furthermore, computational analyses provided further confirmation of the catalytic activity and revealed that the electron transfer from FeNi alloy nanoparticles to the carbon shells activates the carbon surface, leading to enhanced catalytic performance. This research not only sheds light on the rational design and synthesis of heteroatom-doped carbon materials supporting the growth-constrained transition metal alloys but also offers a practical solution for advancing the application of Zn-air batteries.

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Adequately stabilized and exposed copper heterostructure for CO2 electroreduction to ethanol with ultrahigh mass activity Xingxing Jiang, Yuxin Zhao, Yan Kong, Jianju Sun, Shangzhao Feng, Qi Hu, Hengpan Yang, Chuanxin He 2024, 58:  216-225.  DOI: 10.1016/S1872-2067(23)64604-2 Abstract ( 98 )   HTML ( 4 )   PDF (1990KB) ( 79 )   Supporting Information Adequately exposure of active sites to reactants is crucial in improving the actual catalytic activity in various electrocatalytic reactions. e.g., CO2 electroreduction. Herein, we construct abundant opening mesopores throughout carbon nanofibers via a simple O2 plasma treatment, which can simultaneously create a CO2-rich environment and expose Cu/CuxO sites to the reaction interface. The unique Cu/CuxO sites can generate a 70.7% Faradaic efficiency of C2H5OH at the 400 mA cm-2 current density. Moreover, this superior structure can significantly increase the number of active sites that actually participated in the reaction, and leads to an exceptional 8.4 A mg-1 Cu mass activity for C2H5OH, which is among the highest mass activity for C2H5OH ever reported. The DFT calculation and CO-TPD studies reveal that the created Cu/CuxO heterostructure provides adequate *CO coverages and lowers the energy barrier of the C-C coupling process for ethanol formation, in which the key ethanol intermediates are detected via the in-situ spectra investigations. This strategy can be easily applied to construct efficient catalysts in other electrocatalytic reactions.

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TEMPO radically expedites the conversion of sulfides to sulfoxides by pyrene-based metal-organic framework photocatalysis Bing Zeng, Fengwei Huang, Yuexin Wang, Kanghui Xiong, Xianjun Lang 2024, 58:  226-236.  DOI: 10.1016/S1872-2067(23)64601-7 Abstract ( 77 )   HTML ( 6 )   PDF (4607KB) ( 34 )   Supporting Information Metal-organic frameworks (MOFs) are well-documented for visible light photocatalysis because of their tailorable structures and tunable absorptions through organic linkers. By employing a highly conjugated linker, 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, the optical absorption of the MOF NU-1100 is effectively tuned to visible light below 600 nm region. Under green light irradiation, NU-1100 triggers charge separation and modulates electron transfer from the linkers to the Zr6O4(OH)412+ clusters, driving the oxidation of sulfides to sulfoxides. Notably, adding a redox mediator radically expedites the oxidation of sulfides by NU-1100 photocatalysis, TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) and 4-carboxy-TEMPO. At least 2.7 and 5.2 times of conversions of phenyl methyl sulfide are achieved by NU-1100 photocatalysis with TEMPO and 4-carboxy-TEMPO, respectively. A series of characterizations illustrate that 4-carboxy-TEMPO is adsorbed onto the exterior surface of Zr6O4(OH)412+ clusters of NU-1100 to mediate hole transfer and achieve higher charge transfer efficiency. Mechanistic studies indicate that superoxide is the essential reactive oxygen species and that the oxidation of sulfides is driven by an electron transfer pathway. This study demonstrates the integration of redox mediators with MOFs can drive more efficient visible light photocatalytic reactions.

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Top-down fabrication of active interface between TiO2 and Pt nanoclusters. Part 1: Redispersion process and mechanism Xiaorui Du, Yike Huang, Xiaoli Pan, Xunzhu Jiang, Yang Su, Jingyi Yang, Yalin Guo, Bing Han, Chengyan Wen, Chenguang Wang, Botao Qiao 2024, 58:  237-246.  DOI: 10.1016/S1872-2067(23)64597-8 Abstract ( 57 )   HTML ( 3 )   PDF (2057KB) ( 37 )   Supporting Information Supported metal nanoclusters (NCs) are regarded as the next generation of catalyst that bridge the nanocatalyst and single-atom catalyst. However, feasible fabrication of thermally stable NCs has remained a daunting challenge. In this paper, the first part of an extended work, we report a simple route to fabricate Pt NCs in size of around 1 nm through redispersion of Pt nanoparticles (NPs) or commercial PtO2 by a calcination treatment. Combining control experiments and detailed DFT simulation, the whole redispersion process was described and evidenced to proceed via a gas-phase trapping way: Under promotion of oxygen atmosphere and high temperature, volatile oxidized Pt monomers were firstly generated and then trapped by surface defects, forming special sites that preferentially induce the growth of clusters on them. The growing clusters have both size- and temperature-dependent stability, resulting a most stable size distribution of around 1 nm when fabricated at 550 °C. This work provides a feasible top-down strategy to fabricate highly dispersed metal clusters.

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Top-down fabrication of active interface between TiO2 and Pt nanoclusters. Part 2: Catalytic performance and reaction mechanism in CO oxidation Xiaorui Du, Yike Huang, Xiaoli Pan, Xunzhu Jiang, Yang Su, Jingyi Yang, Yalin Guo, Bing Han, Chengyan Wen, Chenguang Wang, Botao Qiao 2024, 58:  247-254.  DOI: 10.1016/S1872-2067(23)64598-X Abstract ( 77 )   HTML ( 5 )   PDF (2642KB) ( 45 )   Supporting Information In this work, following Part 1 that has found a redispersion process from Pt nanoparticles (NPs, about 3.4 nm) to nanoclusters (NCs, about 1 nm) on TiO2 and elucidated its mechanism, we carefully investigated the catalytic performance of the obtained Pt NC catalyst in CO oxidation as well as the corresponding reaction mechanism. The Pt NC catalyst excels than its parent catalyst in terms of both intrinsic and apparent activity. Detailed studies by combining kinetic measurements, isotopic labeling reaction experiments, and low-temperature operando FT-IR unambiguously demonstrated that the Pt NCs deposited on TiO2 can form unique interfacial sites that enable to active O2 at very low temperature, thus the CO adsorbed on TiO2 can diffuses to, and reacts with, the activated oxygen, rendering a high activity at low temperatures. This work is contributory in understanding the origin of the high activity of the supported metal cluster catalysts.