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Chinese Journal of Catalysis
2024, Vol. 56
Online: 18 January 2024

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Cover: Professors Zhiliang Jin, Xin Li, and co-workers have developed a new strategy to construct both reduction and oxidation sites to overcome the effective separation and utilization of photogenerated electron-hole pairs. The introduction of graphdiyne with adjustable electronic structure into CuMn2O4 with oxidation site improves the recombination of photogenerated electron-hole pairs to a great extent, and provides a novel approach for efficient photocatalytic hydrogen production. Read more about the article behind the cover on page 88–103.

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Perspectives

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General definition of hydrogen energy and related electrochemical technologies Gongwei Wang, Li Xiao, Lin Zhuang 2024, 56:  1-8.  DOI: 10.1016/S1872-2067(23)64572-3 Abstract ( 278 )   HTML ( 48 )   PDF (13078KB) ( 213 )   Electrochemical energy conversion, based on the transformation between electrical energy and chemical energy, is crucial for the storage and utilization of renewable electrical energy, as well as the eco-friendly production of valuable fuels and chemicals. Here we put forward a general definition of hydrogen energy that covers the energy storage/release in any hydrogen-involved chemical bonds, such as H-H, C-H, and N-H bonds. Given that H2 gas, hydrocarbons, and hydronitrogens are not only high-energy-density fuels but also important industrial feedstocks, the successful implementation of efficient energy storage/release in the H-H (hydrogen cycle), C-H (carbon cycle), and N-H (nitrogen cycle) bonds are of great significance in establishing sustainable energy systems and reducing dependence on fossil fuels, which contributes to address global energy crisis and environmental problems. We provide a concise overview of the current development status of some key low-temperature (< 100 °C) electrochemical technologies relevant to general hydrogen energy, including fuel cells, water electrolysis, CO2 electrolysis, and N2 electrolysis. This discussion aims to elucidate the major challenges and future trends in this field.

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A perspective on interface engineering of transition metal dichalcogenides for high-current-density hydrogen evolution Xin Kang, Qiangmin Yu, Tianhao Zhang, Shuqi Hu, Heming Liu, Zhiyuan Zhang, Bilu Liu 2024, 56:  9-24.  DOI: 10.1016/S1872-2067(23)64571-1 Abstract ( 276 )   HTML ( 34 )   PDF (5502KB) ( 129 )   abstract: Water electrolysis for green hydrogen production is important for the global carbon neutrality. The industrialization of this technology requires efficient and durable electrocatalysts under high-current-density (HCD) operations. However, the insufficient mass and charge transfer at the various interfaces lead to unsatisfactory HCD activity and durability. Interface engineering is important for designing efficient HCD electrocatalysts. In this perspective, we analyze the processes taking place at three interfaces including the catalyst-substrate, catalyst-electrolyte, and catalyst-gas interfaces, and reveal the correlations between interface interactions and the challenges for HCD electrolysis. We then highlight the development of HCD electrocatalysts that focus on interface engineering using the example of transition metal dichalcogenide based catalysts, which have attracted widespread interests in recent years. Finally, we give an outlook on the development of interface engineering for the industrialization of water electrolysis technology.

Reviews

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Metal-based electrocatalysts for ammonia electro-oxidation reaction to nitrate/nitrite: Past, present, and future Yunrui Tian, Haotian Tan, Xia Li, Jingjing Jia, Zixian Mao, Jian Liu, Ji Liang 2024, 56:  25-50.  DOI: 10.1016/S1872-2067(23)64576-0 Abstract ( 463 )   HTML ( 30 )   PDF (8718KB) ( 222 )   abstract: Electrocatalytic oxidation of ammonia is an appealing, low-temperature process for the sustainable production of nitrites/nitrates that avoids the formation of pernicious N2O and can be fully powered by renewable electricity. However, the number of known efficient catalysts for this purpose is limited. In this review, based on the possible reaction mechanism of electrocatalytic ammonia oxidation reaction (AOR), the control of catalyst performance by hybrid composite design, microstructure construction, and surface modification is reviewed, and the prospects of AOR catalysts for photocatalysis, thermocatalysis, and biocatalysis are proposed. Notably, a rational and rigorous AOR experimental protocol is suggested. We hope that the research community will jointly focus on the sensible testing of AOR products and eventually develop a more realistic evaluation system. Finally, a techno-economic analysis of AOR electrocatalysis was carried out, and a more economical carbon-free cycle system based on the AOR process was proposed.

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Enhancing the performance of platinum group metal-based electrocatalysts through nonmetallic element doping Yiping Li, Tanyuan Wang, Zhangyi Yao, Qi’an Chen, Qing Li 2024, 56:  51-73.  DOI: 10.1016/S1872-2067(23)64569-3 Abstract ( 379 )   HTML ( 18 )   PDF (15194KB) ( 131 )   abstract: Platinum group metal (PGM) catalysts have been well recognized as one of the best catalysts towards energy conversion and storage devices, such as fuel cells and water electrolyzers. Nevertheless, their commercial applications are strictly limited by the unsatisfactory catalytic activity and stability. Recently, nonmetallic (H, B, C, N, P, S, etc.) atoms doping is explored to be an efficient strategy to optimize the catalytic activity and durability of PGM-based catalysts via precisely electronic and coordination structure modulation, thus arising tremendous attention. However, systematical discussions on this topic is still lacking. In this review, the representative progresses of nonmetal elements doped PGM-based electrocatalysts for different electrocatalytic reactions are summarized. Firstly, this review discusses the key factors that affect the activity and stability of the catalysts, and introduces the basic principles of nonmetal-doping for improving the performance of PGM-based catalysts. Secondly, advanced characterization techniques and theoretical calculations are highlighted respectively for revealing the activity enhancement mechanism. Then the synthesis methods to incorporate the nonmetals are listed, intending to provide inspirations for the future design of materials. The promising modification strategies for tuning the active species are further proposed. Afterwards, an overview of nonmetal-doped PGM-based catalysts is provided for the electrocatalytic applications, with an emphasis on revealing the structure-performance relationship. Finally, further developments and challenges involving synthesis, mechanism analysis, new materials as well as reactions, stability issues and practical applications are outlined, aiming to promote the in-depth research on advanced PGM-based catalysts.

Communications

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Photocatalytic carboxylation of styrenes with CO2 via C=C double bond cleavage Ke-Gong Cao, Tian-Yu Gao, Li-Li Liao, Chuan-Kun Ran, Yuan-Xu Jiang, Wei Zhang, Qi Zhou, Jian-Heng Ye, Yu Lan, Da-Gang Yu 2024, 56:  74-80.  DOI: 10.1016/S1872-2067(23)64583-8 Abstract ( 413 )   HTML ( 25 )   PDF (1284KB) ( 206 )   Supporting Information Catalytic cleavage of C=C double bonds in alkenes is highly important to convert feedstocks into high-value compounds. However, these approaches are mainly limited to oxidative cleavage of alkenes with excess oxidants and redox-neutral alkene metathesis. In contrast, reductive C=C double bond cleavage and functionalization have not been reported. Herein, we report a novel visible-light photoredox-catalyzed carboxylation of styrenes with CO2 via reductive C=C double bond cleavage. The use of dicyclohexylmethylamine as scission reagent is the key to the success. Different from previous homologation reactions with CO2, this protocol enabled exchange of the carbon of styrenes with CO2, affording important aryl acetic acids via C=C double bond cleavage. Moreover, preliminary mechanistic investigation and DFT calculations shed light on the reaction mechanism, disclosing aminomethyl-carboxylation intermediate, benzylic radicals and carbanions as key intermediates in the reaction.

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A novel core-shell nanostructure of Ti-Au nanocrystal with PtNi alloy skin: Enhancing the durability for oxygen reduction reaction Giday Fisseha, Ya’nan Yu, Shaojie Lu, Yiping Hu, Yu Zhou, Qin Yue 2024, 56:  81-87.  DOI: 10.1016/S1872-2067(23)64568-1 Abstract ( 261 )   HTML ( 16 )   PDF (2874KB) ( 101 )   Supporting Information The sluggish oxygen reduction reaction (ORR) at the cathode largely hinders the practical application of the proton-exchange membrane fuel cells (PEMFCs). Pt-based nanocrystals are the most effective electrocatalysts for the oxygen reduction reaction, however, suffer high cost, scarcity and unsatisfied durability. Herein, we report a new category of annealed multimetallic core-shell catalyst of gold core doped with titanium and platinum-nickel (PtNi) shell with Pt-rich surface as a highly active and robust electrocatalyst for ORR. The introduction of titanium can effectively stabilize the gold core, avoiding the outward migration of Au atoms and ensuring the exposure of Pt-Ni active sites. The experimental findings revealed that the annealed Ti-Au@PtNi NPs catalyst provides 19.26 and 9.84 times higher mass and specific activities than commercial Pt/C catalysts for the oxygen reduction reaction. Moreover, durability tests of annealed Ti-Au@PtNi NPs show no noticeable activity loss even after 20000 potential cycles between 0.6 and 1.0 V vs. RHE, demonstrating a promising catalyst for the oxygen reduction reaction.

Articles

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Anchoring oxidation co-catalyst over CuMn2O4/graphdiyne S-scheme heterojunction to promote eosin-sensitized photocatalytic hydrogen evolution Cheng Yang, Xin Li, Mei Li, Guijie Liang, Zhiliang Jin 2024, 56:  88-103.  DOI: 10.1016/S1872-2067(23)64563-2 Abstract ( 223 )   HTML ( 21 )   PDF (7285KB) ( 141 )   It is widely acknowledged that efficient charge separation and utilization of photocatalysts are key factors in determing the photocatalytic hydrogen production. Construction of heterojunction has been considered as a promising way to efficiently solve the spatial separation of photogenerated charges. In addition, the introduction of proper cocatalysts can realize the separation of electrons and holes of the photocatalyst and enhance the photocatalytic performance by promoting more carriers to flow to the corresponding active sites. Herein, the S-scheme heterojunction was constructed by introducing graphdiyne into CuMn2O4 for photocatalytic hydrogen evolution. Graphdiyne as a reduction semiconductor and in situ produced Mn2O3 from CuMn2O4 as an oxidation cocatalyst to promote the precisely migration of photogenerated electrons and holes to the corresponding reduction and oxidation sites of photocatalyst. Notably, the photocatalytic performance of the 600-CuMn2O4/GDY-40%（6-CG-40%）could reach 1586.54 μmol g-1 h-1, which is 13.86 and 21.48 times higher than those of CuMn2O4 (106.73 μmol g-1 h-1) and graphdiyne (70.57 μmol g-1 h-1), respectively. Theoretical calculations and experiments results show that both in-situ induced growth of Mn2O3 oxidation co-catalyst and the introduction of graphdiyne to construct S-scheme heterojunction efficiently suppress the severe recombination of photogenerated electron-hole pairs, thus optimizing the photogenerated carrier transfer efficiency, and ultimately leading to the enhanced eosin Y-sensitized photocatalytic hydrogen evolution activity. This work provides a promising method for the construction of oxidation cocatalyst engineered S-scheme heterojunction for solar water splitting.

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Synergistic catalytic conversion of nitrate into ammonia on copper phthalocyanine and FeNC two-component catalyst Yi Wang, Shuo Wang, Yunfan Fu, Jiaqi Sang, Yipeng Zang, Pengfei Wei, Hefei Li, Guoxiong Wang, Xinhe Bao 2024, 56:  104-113.  DOI: 10.1016/S1872-2067(23)64578-4 Abstract ( 296 )   HTML ( 18 )   PDF (3654KB) ( 137 )   Supporting Information Cu-based catalysts have been extensively studied to enhance the performance of the electrochemical nitrate reduction reaction (NO3−RR), while it is still a challenge to balance high ammonia (NH3) current density and Faradaic efficiency. Here, we incorporated nitrogen coordinated iron single atom catalyst (FeNC) with copper phthalocyanine (CuPc), denoted as CuPc/FeNC, for NO3−RR. Compared with the two individual catalysts, this two-component catalyst increases NH3 Faradaic efficiency and current density at low overpotentials, achieves efficient synergistic catalytic conversion. Experiments and theoretical calculations reveal that the enhanced electrochemical performance of CuPc/FeNC catalyst comes from the tandem process, in which NO2‒ is produced on CuPc and then transferred to FeNC and further reduced to NH3. In this exceptional tandem catalyst system, an outstanding NH3 Faradaic efficiency close to 100% was achieved at potentials greater than −0.35 V vs. RHE, coupled with a peak NH3 partial current density of 273 mA cm‒2 at −0.57 V vs. RHE, effectively suppressing NO2‒ production across the entire potential range. This strategy provides a design platform for the continued advancement of NO3‒RR catalysts.

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Adjusting Al location in the framework of ITH zeolites for catalytic conversion of methanol to olefins Kai Fan, Qinming Wu, Shuo Liu, Haiyu Kong, Sen Wang, Eduard Kunkes, Trees De Baerdemaeker, Andrei-Nicolae Parvulescu, Nils Bottke, Toshiyuki Yokoi, Dirk E. De Vos, Xiangju Meng, Weiping Zhang, Feng-Shou Xiao 2024, 56:  114-121.  DOI: 10.1016/S1872-2067(23)64574-7 Abstract ( 228 )   HTML ( 15 )   PDF (6276KB) ( 86 )   Supporting Information Adjusting location and distribution of Al sites in the zeolite framework is critical for catalysis, and typical strategies include using zeolites as starting Al source. However, this approach is still challenging for aluminosilicate ITH zeolite. Herein, the distribution of Al species in the framework of ITH was efficiently regulated by implementing LTA zeolite as the aluminum source added in the starting gels (LTA-ITH). The obtained LTA-ITH zeolites have similar nanosheet morphology, textual parameters, and acidic properties to those of conventional ITH synthesized from boehmite (C-ITH), while the results of 27Al MAS NMR spectra and 1-hexene cracking indicate that they have a different Al distribution. The use of LTA zeolite in starting gel is favorable for the formation of more Al species in sinusoidal and straight channels, compared with the C-ITH. Catalytic tests in the conversion of methanol to light olefin showed that LTA-ITH exhibited enhanced catalyst lifetime and propene selectivity compared with the C-ITH, which is reasonably attributed to the different locations of Al species in their respective ITH frameworks.

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Direct synthesis of α,ω-dicarboxylic acids via dicarbonylation of cyclic ethers Changpo Ma, Ying Lai, Tiange Zhao, Xiaoxuan Zhang, Haichao Liu, Weiran Yang 2024, 56:  122-129.  DOI: 10.1016/S1872-2067(23)64577-2 Abstract ( 381 )   HTML ( 14 )   PDF (2015KB) ( 83 )   Supporting Information α,ω-Dicarboxylic acids are important intermediates for the preparation of polyamides, polyesters and polyurethanes. However, their production pathways are limited and usually suffer from low efficiency and environmental problems. Here, we report an innovative approach to synthesize C+2 dicarboxylic acids directly from cyclic ethers by dicarbonylation. Different from the general findings that C+1 monocarboxylic acids are produced by carbonylation of cyclic ethers involving alkene intermediates, in this work, by manipulating the reaction system with RhCl3 and iodine in acetic acid, diiodide-substituted intermediates were selectively formed and subsequently converted to dicarboxylic acids in the presence of H2 and CO. As high as 84% yield of adipic acid was obtained directly from tetrahydrofuran. This catalytic system is applicable not only to a wide variety of cyclic ethers but also to different primary diols to synthesize C2-elongated α,ω-dicarboxylic acids. This work provides a novel dicarbonylation strategy for the efficient synthesis of adipic acid, glutaric acid and other important α,ω-dicarboxylic acids (such as 1,7-heptanedioic acid and 1,8-octanedioic acid) that are still not easily synthesized by other methods.

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Electronic perturbation-promoted interfacial pathway for facile C-H dissociation Zhe Wang, Chunpeng Wang, Bing Lu, Zhirong Chen, Yong Wang, Shanjun Mao 2024, 56:  130-138.  DOI: 10.1016/S1872-2067(23)64575-9 Abstract ( 274 )   HTML ( 11 )   PDF (2734KB) ( 110 )   Supporting Information Interface has often played significant role in the behavior of metal-based catalysts during various heterogeneous reactions. Herein, we reported a novel interfacial pathway for propane dehydrogenation on Pt-GaOx dual sites. The active ensemble, composing Pt particles and Ga2O3 clusters, facilitates the facile dissociation of C‒H bonds (energy barrier < 0.30 eV) through H-abstraction by O sites, coupled with alkyl stabilization on the Pt surface. Notably, the electronic perturbation of the Pt slab induces higher-lying O 2p states at the interface, accompanied by a substantial density of states around fermi level. This is in stark contrast to the O species present in Ga2O3 crystals or clusters alone, leading to an exceptionally strong affinity for H and a robust ability for C-H scission. The Pt/Ga-Al2O3 catalysts prepared with Pt nanoparticles decorated by Ga oxide exhibit superior performance compared to Pt/Al2O3 and PtSn/Al2O3 catalysts. This insight into interfacial catalysis contributes to a broader understanding of the origin of the high catalytic efficiency observed in metal-based catalysts.

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Promoting electrocatalytic oxidation of methanol to formate through interfacial interaction in NiMo oxide-CoMo oxide mixture-derived catalysts Yanbin Qi, Yihua Zhu, Hongliang Jiang, Chunzhong Li 2024, 56:  139-149.  DOI: 10.1016/S1872-2067(23)64565-6 Abstract ( 221 )   HTML ( 17 )   PDF (4631KB) ( 99 )   Supporting Information Designing efficient, stable, and easily scaled-up catalysts for nucleophile oxidation reactions (NOR) is a key step in promoting the industrial application of NOR. Here, a simple physical mixing strategy is adopted to prepare a mixture of NiMo oxide and CoMo oxide as catalyst for methanol electrocatalytic oxidation reaction (MOR). The mixture exhibits high catalytic activity for MOR and its performance far exceeds that of a single component. The interaction at the contact interface between nickel and cobalt components is clarified through operando electrochemical impedance spectroscopy, in-situ Raman spectroscopy, and a series of electrochemical tests. The interfacial interaction enhances the charge transport and promotes the formation of electrophilic OH* species, which significantly boosts the methanol oxidation reaction. This work provides a new idea for the design of efficient and easily scaled-up catalysts for nucleophile oxidation reactions.

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Electronic state, abundance and microenvironment modulation of Ru nanoclusters within hierarchically porous UiO-66(Ce) for efficient hydrogenation of dicyclopentadiene Rushuo Li, Linmeng Wang, Peiyun Zhou, Jing Lin, Zhiyuan Liu, Juan Chen, Danfeng Zhao, Xiubing Huang, Zhiping Tao, Ge Wang 2024, 56:  150-165.  DOI: 10.1016/S1872-2067(23)64562-0 Abstract ( 309 )   HTML ( 15 )   PDF (9458KB) ( 103 )   Supporting Information Developing catalysts for dicyclopentadiene (DCPD) hydrogenation to tetrahydrodicyclopentadiene (THDCPD) at low temperature is crucial and challenging for the green and energy-saving production of high energy density aviation fuel. Herein, hierarchically porous UiO-66(Ce) encapsulate Ru nanoclusters (NCs) was successfully customized by soft template method and in-situ reduction. The mesoporous UiO-66(Ce) promoted the high dispersion of Ru NCs, and the transfer of substrate molecules. By controlling the synthesis conditions, the electronic state, abundance, and microenvironment of Ru NCs were precisely regulated. Theory calculation and experimental results revealed that metallic Ru as the main active sites greatly promoted the adsorption and activation of substrate molecules. Therefore, mesoporous UiO-66(Ce) encapsulated Ru NCs showed remarkable catalytic DCPD hydrogenation performance with DCPD conversion of 100% and THDCPD selectivity of ~100% (60 °C, only 35 min). This study has brought new inspiration and guidance to the rational design of function materials for various catalytic applications.

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PO43- coordinated Co2+ species on yttrium phosphate boosting the valorization of ethanol to butadiene Bai-Chuan Zhou, Wen-Cui Li, Jia Wang, Dan-Hui Sun, Shi-Yu Xiang, Xin-Qian Gao, An-Hui Lu 2024, 56:  166-175.  DOI: 10.1016/S1872-2067(23)64567-X Abstract ( 261 )   HTML ( 24 )   PDF (4187KB) ( 121 )   Supporting Information Upgrading of sustainable ethanol into C4 olefins by C-C coupling contributes to alleviating the dependency towards petroleum. The reaction network consists several key steps, whereas dehydration often competes with dehydrogenation over acidic catalyst. Herein, we report a designed bifunctional Co-YPO4 catalyst with balanced active sites for dehydrogenation and condensation that can directly catalyze ethanol to butadiene. The YPO4 can stabilize Co2+ species to form highly dispersed [Co-O-P] sites, which catalyze ethanol dehydrogenation to acetaldehyde. Additionally, the YPO4 surface exposed Y3+ site, as Lewis acid center, which can effectively catalyze C-C coupling reaction. The addition of cobalt enhances the ethanol dehydrogenation process while reducing the surface acidity, thus inhibiting the formation of dehydration products and promoting the formation of butadiene. Kinetic measurements suggest that the rate-limiting step is the dehydrogenation of ethanol to acetaldehyde. The synthesized Co-YPO4 shows a 68.5% selectivity of butadiene under a conversion of 78.2% at 350 °C and a weight hourly space velocity of 1.0 gC2H5OH•gCat.-1•h-1.

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Uleashing efficient and CO-resilient alkaline hydrogen oxidation of Pd3P through phosphorus vacancy defect engineering Yuting Yang, Luyan Shi, Qinrui Liang, Yi Liu, Jiaxin Dong, Tayirjan Taylor Isimjan, Bao Wang, Xiulin Yang 2024, 56:  176-187.  DOI: 10.1016/S1872-2067(23)64570-X Abstract ( 324 )   HTML ( 32 )   PDF (4052KB) ( 113 )   Supporting Information A high-performance and highly CO-resilient hydrogen oxidation reaction (HOR) electrocatalyst is heralded as core material to solve the commercial deployment of hydrogen fuel cells. Phosphorus vacancies, as a type of delicate point defect, could effectively and flexibly modulate the catalytic performance. Therefore, based on the vacancy design philosophy of “less is more”, we synthesize a phosphorus-vacancy-rich Pd3P@C (Vp-Pd3P@C) catalyst with bowl-like hemisphere structure for alkaline HOR, for the first time. The Vp-Pd3P@C catalyst exhibits remarkable mass activity and exchange current density of 1.66 mA μgPd-1 and 3.2 mA cm-2, respectively, surpassing those of Pd3P@C (0.45 mA μgPd-1, 1.78 mA cm-2) and commercial Pt/C (0.3 mA μgPt-1, 2.29 mA cm-2). Intriguingly, the catalyst can tolerate 1000 ppm CO that Pt/C catalyst lacks. Density functional theory calculations uncover that the optimal local coordination environment and favorable electronic structure that rooted from phosphorus vacancy enable optimum adsorption kinetics of hydrogen and hydroxyl while concomitantly suppressing Pd 4d → CO 2π* back donation, contributing to the remarkable HOR reactivity and CO tolerance.