Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64836-4
Chenjia Liang , Jun Yao , Ningze Gao , Xiaoxia Hou , Haoyu Lu , Ruiyao Zhao , Ziheng Zhuang , Jie Yang , Liwen Wang , Xiangke Guo , Nianhua Xue , Tao Wang , Yan Zhu , Weiping Ding
For achieving high-power and low-platinum direct methanol fuel cell (DMFC) under proton-exchange-membrane, we introduce the oxidation-state ruthenium species as H2O-activation centers stabilized on PtZn NPs to boost methanol-oxidation reaction (MOR). The Zn-regulated Ru centers, approaching bivalent states, enhance interfacial H2O-capture/dissociation and OH-transfer, enabling rapid CO* removal from adjacent Pt sites. It exhibits an outstanding mass activity of MOR at 2.71 A mgPt−1 and powers a DMFC with 191.2 mW cm−2 peak density (382.4 W gPt−1) while maintaining 125-hour stability, higher than documented results to date, essentially different from traditional alloy catalysts. Combined ab initio molecular dynamics simulations and in-situ spectroscopy reveal a dense O-down water network around Ru centers, where intermediate RuO(OH)2 structure significantly deceases the H2O-dissociation barrier. Kinetic isotope effect tests (CH3OH/H2O vs. D2O) show JH2O/D2O = 4.2 for RuOx-PtZn/C at 0.85 VRHE, versus 16.2 for RuOx-Pt/C, directly confirming superior water activation efficiency of RuOx-PtZn/C. We envision that the comprehensive understanding of high-performance MOR on RuOx-PtZn/C through experimental-theoretical approaches will contribute to the practical application of DMFC as early as possible.
为了实现质子交换膜下大功率低铂直接甲醇燃料电池（DMFC），我们引入氧化态钌作为稳定在PtZn NPs上的h2o活化中心，以促进甲醇氧化反应（MOR）。zn调节的Ru中心接近二价态，增强了界面的h2o捕获/解离和oh转移，使CO*能够从邻近的Pt位点快速去除。它在2.71 A mgPt−1时表现出优异的MOR质量活性，并为DMFC提供191.2 mW cm−2峰值密度（382.4 W gPt−1）的动力，同时保持125小时的稳定性，高于迄今为止记录的结果，与传统合金催化剂本质上不同。结合从头算分子动力学模拟和原位光谱分析表明，在Ru中心周围存在一个密集的O-down水网络，其中中间的RuO(OH)2结构显著降低了h2o -解离屏障。动力学同位素效应测试（CH3OH/H2O vs. D2O）显示，在0.85 VRHE条件下，RuOx-PtZn/C的JH2O/D2O = 4.2，而RuOx-Pt/C的JH2O/D2O = 16.2，直接证实了RuOx-PtZn/C具有优越的水活化效率。我们期望通过实验-理论方法对RuOx-PtZn/C上高性能MOR的全面理解将有助于DMFC的尽早实际应用。
{"title":"RuOx-PtZn catalyst boosting methanol electro-oxidation by synergic water-activation for high-performance direct methanol fuel cell","authors":"Chenjia Liang , Jun Yao , Ningze Gao , Xiaoxia Hou , Haoyu Lu , Ruiyao Zhao , Ziheng Zhuang , Jie Yang , Liwen Wang , Xiangke Guo , Nianhua Xue , Tao Wang , Yan Zhu , Weiping Ding","doi":"10.1016/S1872-2067(25)64836-4","DOIUrl":"10.1016/S1872-2067(25)64836-4","url":null,"abstract":"<div><div>For achieving high-power and low-platinum direct methanol fuel cell (DMFC) under proton-exchange-membrane, we introduce the oxidation-state ruthenium species as H<sub>2</sub>O-activation centers stabilized on PtZn NPs to boost methanol-oxidation reaction (MOR). The Zn-regulated Ru centers, approaching bivalent states, enhance interfacial H<sub>2</sub>O-capture/dissociation and OH-transfer, enabling rapid CO* removal from adjacent Pt sites. It exhibits an outstanding mass activity of MOR at 2.71 A mg<sub>Pt</sub><sup>−1</sup> and powers a DMFC with 191.2 mW cm<sup>−2</sup> peak density (382.4 W g<sub>Pt</sub><sup>−1</sup>) while maintaining 125-hour stability, higher than documented results to date, essentially different from traditional alloy catalysts. Combined ab initio molecular dynamics simulations and <em>in-situ</em> spectroscopy reveal a dense O-down water network around Ru centers, where intermediate RuO(OH)<sub>2</sub> structure significantly deceases the H<sub>2</sub>O-dissociation barrier. Kinetic isotope effect tests (CH<sub>3</sub>OH/H<sub>2</sub>O <em>vs</em>. D<sub>2</sub>O) show <em>J</em><sub>H2O/D2O</sub> = 4.2 for RuO<sub><em>x</em></sub>-PtZn/C at 0.85 V<sub>RHE</sub>, versus 16.2 for RuO<sub><em>x</em></sub>-Pt/C, directly confirming superior water activation efficiency of RuO<sub><em>x</em></sub>-PtZn/C. We envision that the comprehensive understanding of high-performance MOR on RuO<sub><em>x</em></sub>-PtZn/C through experimental-theoretical approaches will contribute to the practical application of DMFC as early as possible.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 304-315"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64883-2
Haopeng Jiang , Jinhe Li , Xiaohui Yu , Huilong Dong , Weikang Wang , Qinqin Liu
To address persistent challenge of charge recombination in semiconductor photocatalysis, we engineered an S-scheme heterojunction via covalent β-ketoenamine bridges between zirconium-based MOFs and triazine-COFs (Zr-BTB-COF). This dual-functional system pioneered a “one-photon, two-value” strategy for simultaneous CO2-to-CO reduction and 4-methoxybenzyl alcohol-to-anisaldehyde oxidation, enabling solar-driven carbon refineries. Synergistic in-situ XPS analysis and density functional theory calculations unambiguously validated the S-scheme charge transfer mechanism. The covalent interface overcame lattice mismatch constraints while Fermi-level alignment generated an enhanced built-in electric field (9.8 times stronger than pristine Zr-BTB-NH2), achieving ultrafast charge separation. Low-energy carrier recombination through the β-ketoenamine bridge preserved high-potential carriers (–1.61 V for CO2 reduction; +2.22 V for alcohol oxidation). Critically, this architecture reduced the activation energy barrier for the rate-limiting *COOH → *CO step to ΔG = 0.65 eV, a 42% reduction versus isolated Zr-BTB-NH2. Through concerted thermodynamic and kinetic optimization, the covalent Zr-BTB-COF achieved high CO and anisaldehyde yields (71.9 and 44.7 μmol·g−1·h−1) with internal quantum efficiency of 3.75% (365 nm). This bond-resolved interface engineering paradigm establishes a new design framework for synchronizing carbon-neutral cycles with high-value chemical synthesis.
{"title":"Interface engineering of covalent β-ketoenamine-bridged S-scheme heterojunction for synergistic solar-powered CO2-to-CO conversion paired with selective alcohol oxidation","authors":"Haopeng Jiang , Jinhe Li , Xiaohui Yu , Huilong Dong , Weikang Wang , Qinqin Liu","doi":"10.1016/S1872-2067(25)64883-2","DOIUrl":"10.1016/S1872-2067(25)64883-2","url":null,"abstract":"<div><div>To address persistent challenge of charge recombination in semiconductor photocatalysis, we engineered an S-scheme heterojunction via covalent <em>β</em>-ketoenamine bridges between zirconium-based MOFs and triazine-COFs (Zr-BTB-COF). This dual-functional system pioneered a “one-photon, two-value” strategy for simultaneous CO<sub>2</sub>-to-CO reduction and 4-methoxybenzyl alcohol-to-anisaldehyde oxidation, enabling solar-driven carbon refineries. Synergistic <em>in-situ</em> XPS analysis and density functional theory calculations unambiguously validated the S-scheme charge transfer mechanism. The covalent interface overcame lattice mismatch constraints while Fermi-level alignment generated an enhanced built-in electric field (9.8 times stronger than pristine Zr-BTB-NH<sub>2</sub>), achieving ultrafast charge separation. Low-energy carrier recombination through the <em>β</em>-ketoenamine bridge preserved high-potential carriers (–1.61 V for CO<sub>2</sub> reduction; +2.22 V for alcohol oxidation). Critically, this architecture reduced the activation energy barrier for the rate-limiting *COOH → *CO step to Δ<em>G</em> = 0.65 eV, a 42% reduction versus isolated Zr-BTB-NH<sub>2</sub>. Through concerted thermodynamic and kinetic optimization, the covalent Zr-BTB-COF achieved high CO and anisaldehyde yields (71.9 and 44.7 μmol·g<sup>−1</sup>·h<sup>−1</sup>) with internal quantum efficiency of 3.75% (365 nm). This bond-resolved interface engineering paradigm establishes a new design framework for synchronizing carbon-neutral cycles with high-value chemical synthesis.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 113-122"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64821-2
Wonjoong Yoon , Malayil Gopalan Sibi , Jaehoon Kim
The direct synthesis of aromatic compounds from the reduction of CO2 remains challenging due to harsh operating conditions, low aromatic yields, and catalyst deactivation. A comprehensive understanding of the distance-induced optimal activity is therefore essential for achieving a rational spatial arrangement of multifunctional active sites for the hydrogenation of CO2 to generate aromatic compounds. In this study, a triple-bed catalyst system is reported, which directly converts CO2 into aromatic compounds with low CO emission levels. At a CO2 conversion of 50.3%, the hydrocarbon pool contained 73.6% aromatic compounds while maintaining a moderately low CO selectivity of 13.9%. The BTEX (benzene, toluene, xylene, and ethylbenzene) selectivity within the aromatic products reached 67.8% and remained stable over 125 h, with only a slight decline being observed beyond this time. Compared to the mortar- and granular-mixed configurations, the triple-bed system exhibited a superior catalytic stability, likely due to the suppression of Na-induced poisoning on the zeolite acid sites. Additionally, the close contact between Fe and the zeolite structure altered the Fe phase evolution process for the chain extension reaction, while also significantly degrading the structural integrity of the zeolite. Under 370 °C and 3.5 MPa conditions, the zeolite crystallinity in the mortar-mixed 11% Na-promoted FeAlOx/Zn-HZSM-5@SiO2 catalyst dropped below 12%, whereas the double- and triple-bed configurations retained crystallinities of ~65%, which likely contributed to the improved catalyst longevity. These results indicate that the triple-bed configuration provides a promising route for enhancing the stability and efficiency of the direct hydrogenation reaction to generate aromatic compounds from CO2.
{"title":"A triple-bed Na-FeAlOx/Zn-HZSM-5@SiO2 catalyst for the stable and direct generation of aromatics via CO2 hydrogenation","authors":"Wonjoong Yoon , Malayil Gopalan Sibi , Jaehoon Kim","doi":"10.1016/S1872-2067(25)64821-2","DOIUrl":"10.1016/S1872-2067(25)64821-2","url":null,"abstract":"<div><div>The direct synthesis of aromatic compounds from the reduction of CO<sub>2</sub> remains challenging due to harsh operating conditions, low aromatic yields, and catalyst deactivation. A comprehensive understanding of the distance-induced optimal activity is therefore essential for achieving a rational spatial arrangement of multifunctional active sites for the hydrogenation of CO<sub>2</sub> to generate aromatic compounds. In this study, a triple-bed catalyst system is reported, which directly converts CO<sub>2</sub> into aromatic compounds with low CO emission levels. At a CO<sub>2</sub> conversion of 50.3%, the hydrocarbon pool contained 73.6% aromatic compounds while maintaining a moderately low CO selectivity of 13.9%. The BTEX (benzene, toluene, xylene, and ethylbenzene) selectivity within the aromatic products reached 67.8% and remained stable over 125 h, with only a slight decline being observed beyond this time. Compared to the mortar- and granular-mixed configurations, the triple-bed system exhibited a superior catalytic stability, likely due to the suppression of Na-induced poisoning on the zeolite acid sites. Additionally, the close contact between Fe and the zeolite structure altered the Fe phase evolution process for the chain extension reaction, while also significantly degrading the structural integrity of the zeolite. Under 370 °C and 3.5 MPa conditions, the zeolite crystallinity in the mortar-mixed 11% Na-promoted FeAlO<sub><em>x</em></sub>/Zn-HZSM-5@SiO<sub>2</sub> catalyst dropped below 12%, whereas the double- and triple-bed configurations retained crystallinities of ~65%, which likely contributed to the improved catalyst longevity. These results indicate that the triple-bed configuration provides a promising route for enhancing the stability and efficiency of the direct hydrogenation reaction to generate aromatic compounds from CO<sub>2</sub>.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 330-346"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64829-7
Shenghui Zhou , Zheng Wang , Voon Huey Lim , Chi Cheng Chong , Hossein Akhoundzadeh , Chao Wu , Mohammadreza Kosari , Shibo Xi , Markus Kraft , Rong Xu
Methylcyclohexane (MCH) stands out as a leading liquid organic hydrogen carrier (LOHC) due to its favorable hydrogen storage capacity and transportability. Despite its potential, advancing catalysts that combine high efficiency, cost-effectiveness, and durability for MCH dehydrogenation to produce hydrogen remains a critical challenge hindering large-scale industrial deployment. Herein, we report the synthesis of highly dispersed and stable bimetallic Pt-MoOx nanoparticles immobilized on γ-Al2O3. The introduction of MoOx species significantly improves the stability of Pt and results in a high toluene (TOL) selectivity of 99.8 % with MCH conversion of 99.5% and a high hydrogen evolution rate of 470.5 mmol·gPt−1·min−1 at 340 °C. Moreover, the optimal catalyst exhibits a remarkable long-term stability, with no evident loss of activity in 140-h dehydrogenation reaction at a weight hourly space velocity of 11.7 h−1. Through detailed in-situ structure analyses, it was revealed that the introduction of subnanometer MoOx species facilitates the generation of ultrafine Pt nanoparticles with improved resistance to sintering, resulting in enhanced catalytic activity and durability of the noble metal. Furthermore, in-situ spectroscopic characterization demonstrates the positively charged Ptδ+ species promote the rapid desorption of TOL products. The excellent catalytic performance including high conversion and selectivity and superior stability offers great opportunities for their practical applications in LOHC technologies.
{"title":"Subnanometer molybdenum oxide-stabilized platinum nanocatalysts enable efficient hydrogen production from methylcyclohexane","authors":"Shenghui Zhou , Zheng Wang , Voon Huey Lim , Chi Cheng Chong , Hossein Akhoundzadeh , Chao Wu , Mohammadreza Kosari , Shibo Xi , Markus Kraft , Rong Xu","doi":"10.1016/S1872-2067(25)64829-7","DOIUrl":"10.1016/S1872-2067(25)64829-7","url":null,"abstract":"<div><div>Methylcyclohexane (MCH) stands out as a leading liquid organic hydrogen carrier (LOHC) due to its favorable hydrogen storage capacity and transportability. Despite its potential, advancing catalysts that combine high efficiency, cost-effectiveness, and durability for MCH dehydrogenation to produce hydrogen remains a critical challenge hindering large-scale industrial deployment. Herein, we report the synthesis of highly dispersed and stable bimetallic Pt-MoO<sub><em>x</em></sub> nanoparticles immobilized on γ-Al<sub>2</sub>O<sub>3</sub>. The introduction of MoO<sub><em>x</em></sub> species significantly improves the stability of Pt and results in a high toluene (TOL) selectivity of 99.8 % with MCH conversion of 99.5% and a high hydrogen evolution rate of 470.5 mmol·g<sub>Pt</sub><sup>−1</sup>·min<sup>−1</sup> at 340 °C. Moreover, the optimal catalyst exhibits a remarkable long-term stability, with no evident loss of activity in 140-h dehydrogenation reaction at a weight hourly space velocity of 11.7 h<sup>−1</sup>. Through detailed <em>in-situ</em> structure analyses, it was revealed that the introduction of subnanometer MoO<sub><em>x</em></sub> species facilitates the generation of ultrafine Pt nanoparticles with improved resistance to sintering, resulting in enhanced catalytic activity and durability of the noble metal. Furthermore, <em>in-situ</em> spectroscopic characterization demonstrates the positively charged Pt<sup><em>δ</em>+</sup> species promote the rapid desorption of TOL products. The excellent catalytic performance including high conversion and selectivity and superior stability offers great opportunities for their practical applications in LOHC technologies.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 347-357"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915450","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64840-6
Binjie Du, Yuhang Xiao, Xiaohong Tan, Weidong He, Yingying Guo, Hao Cui, Chengxin Wang
Tandem electrocatalysis offers considerable potential for selectively converting nitrate ions (NO3−) to ammonia (NH3) via electrochemical reduction, yet its practical application is often hampered by sluggish nitrite ions (NO2−) intermediate transfer between spatially separated active sites and mismatched reaction potentials, which together constrain conversion efficiency and limit high Faradaic efficiency (FE) to a narrow operating window. Herein, we report a rationally designed dual-phase Cu-doped Co/CoO (Cu-Co/CoO) heterojunction, featuring spatially distinct yet synergistic active sites and abundant atomic-scale heterointerfaces that enable accelerated tandem catalysis. Mechanistic investigations reveal that the Cu-doped CoO domain predominantly catalyzes the reduction of NO3− to NO2−, which is rapidly transferred across the heterointerface to the Cu-doped Co domain for further hydrogenation to NH3. As a result, the Cu-Co/CoO catalyst achieves a high FE exceeding 85% and sustains high NH3 yields across a broad potential range. Notably, the catalyst achieves a remarkable NH₃ yield of 27.3 mmol h−1 mgcat−1 and an NH3 partial current density of 0.58 A cm−2 at –0.8 V (vs. RHE). Integration into a Zn-NO3− battery system further enables simultaneous high-rate NH3 production and power output. This work establishes a viable methodology for engineering high-performance tandem electrocatalysts and offers new insights into interfacial engineering for renewable NH3 synthesis.
串联电催化为硝酸离子（NO3−）通过电化学还原选择性转化为氨（NH3）提供了相当大的潜力，但其实际应用往往受到亚硝酸盐离子（NO2−）在空间分离的活性位点之间缓慢的中间转移和不匹配的反应电位的阻碍，这些因素共同限制了转化效率并限制了高法拉第效率（FE）的狭窄操作窗口。在此，我们报告了一个合理设计的双相cu掺杂Co/CoO （Cu-Co/CoO）异质结，具有空间上不同但协同的活性位点和丰富的原子尺度异质界面，可以加速串联催化。机理研究表明，cu掺杂的CoO结构域主要催化NO3−还原为NO2−，NO2−通过异质界面迅速转移到cu掺杂的Co结构域，进一步加氢生成NH3。结果，Cu-Co/CoO催化剂达到了超过85%的高FE，并在很宽的电位范围内保持了高NH3产率。值得注意的是，该催化剂在-0.8 V（相对于RHE）下NH3的产率为27.3 mmol h−1 mgcat−1，NH3的分电流密度为0.58 a cm−2。集成到Zn-NO3 -电池系统中进一步实现同时高速NH3生产和功率输出。本研究为高性能串联电催化剂的工程设计提供了一种可行的方法，并为可再生NH3合成界面工程提供了新的见解。
{"title":"Dual-phase Cu-Co/CoO heterojunctions for efficient tandem nitrate electroreduction via smooth intermediate handover","authors":"Binjie Du, Yuhang Xiao, Xiaohong Tan, Weidong He, Yingying Guo, Hao Cui, Chengxin Wang","doi":"10.1016/S1872-2067(25)64840-6","DOIUrl":"10.1016/S1872-2067(25)64840-6","url":null,"abstract":"<div><div>Tandem electrocatalysis offers considerable potential for selectively converting nitrate ions (NO<sub>3</sub><sup>−</sup>) to ammonia (NH<sub>3</sub>) <em>via</em> electrochemical reduction, yet its practical application is often hampered by sluggish nitrite ions (NO<sub>2</sub><sup>−</sup>) intermediate transfer between spatially separated active sites and mismatched reaction potentials, which together constrain conversion efficiency and limit high Faradaic efficiency (FE) to a narrow operating window. Herein, we report a rationally designed dual-phase Cu-doped Co/CoO (Cu-Co/CoO) heterojunction, featuring spatially distinct yet synergistic active sites and abundant atomic-scale heterointerfaces that enable accelerated tandem catalysis. Mechanistic investigations reveal that the Cu-doped CoO domain predominantly catalyzes the reduction of NO<sub>3</sub><sup>−</sup> to NO<sub>2</sub><sup>−</sup>, which is rapidly transferred across the heterointerface to the Cu-doped Co domain for further hydrogenation to NH<sub>3</sub>. As a result, the Cu-Co/CoO catalyst achieves a high FE exceeding 85% and sustains high NH<sub>3</sub> yields across a broad potential range. Notably, the catalyst achieves a remarkable NH₃ yield of 27.3 mmol h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> and an NH<sub>3</sub> partial current density of 0.58 A cm<sup>−2</sup> at –0.8 V (<em>vs</em>. RHE). Integration into a Zn-NO<sub>3</sub><sup>−</sup> battery system further enables simultaneous high-rate NH<sub>3</sub> production and power output. This work establishes a viable methodology for engineering high-performance tandem electrocatalysts and offers new insights into interfacial engineering for renewable NH<sub>3</sub> synthesis.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 270-281"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64831-5
Shutao Li , Kewei Zeng , Zixuan Li , Xiangming Li , Fang Chen , Hongwei Huang
Photoelectrochemical (PEC) CH3OH oxidation provides a promising path to HCHO synthesis instead of thermal catalytic method. However, it suffers the low conversion rate and selectivity. Here, surface fluorinated BiVO4 photoanodes were fabricated by combined immersion method and PEC treatment for selective CH3OH oxidation into HCHO. The surface fluorination simultaneously improved the reaction kinetics and selectivity for HCHO synthesis on BiVO4 photoanode, where the formation of metal‒F bonds promoted the CH3OH molecules adsorption, O‒H bond stretching, C‒H bond activation, and eventually HCHO desorption, resulting in excellent HCHO production with high selectivity. The optimal photoanode BVO-F2 obtained a photocurrent density of 3.24 mA cm−2 at 1.2 VRHE, which is about twice that of the bulk BVO photoanode (1.66 mA cm−2). In addition, at 0.8VRHE, the Faraday efficiency of BVO-F2 PEC CH3OH oxidation for HCHO synthesis reached 90.7%, and maintained relatively stable performance in continuous oxidation for 5 h, and finally accumulated 98.12 µmol HCHO. This work illustrates the potential of surface functionalization in PEC conversion of small molecules, as well as in regulating charge dynamics and catalytic reaction thermodynamics.
光电化学（PEC）氧化CH3OH为取代热催化法合成HCHO提供了一条很有前途的途径。但是，它的转化率和选择性较低。本研究采用浸渍法和PEC相结合的方法制备了表面氟化BiVO4光阳极，选择性地将CH3OH氧化成HCHO。表面氟化同时提高了BiVO4光阳极上合成HCHO的反应动力学和选择性，其中金属- f键的形成促进了CH3OH分子的吸附、O-H键的拉伸、C-H键的活化，最终促进了HCHO的脱附，从而产生了高选择性的HCHO。最佳光阳极BVO- f2在1.2 VRHE下获得的光电流密度为3.24 mA cm - 2，是本体BVO光阳极（1.66 mA cm - 2）的两倍左右。此外，在0.8VRHE条件下，BVO-F2 PEC CH3OH氧化合成HCHO的法拉第效率达到90.7%，并在连续氧化5h时保持相对稳定的性能，最终积累98.12µmol HCHO。这项工作说明了表面功能化在小分子PEC转化中的潜力，以及在调节电荷动力学和催化反应热力学方面的潜力。
{"title":"Metal-F bond induced by surface fluorination promotes photoelectrochemical selective oxidation of CH3OH to HCHO","authors":"Shutao Li , Kewei Zeng , Zixuan Li , Xiangming Li , Fang Chen , Hongwei Huang","doi":"10.1016/S1872-2067(25)64831-5","DOIUrl":"10.1016/S1872-2067(25)64831-5","url":null,"abstract":"<div><div>Photoelectrochemical (PEC) CH<sub>3</sub>OH oxidation provides a promising path to HCHO synthesis instead of thermal catalytic method. However, it suffers the low conversion rate and selectivity. Here, surface fluorinated BiVO<sub>4</sub> photoanodes were fabricated by combined immersion method and PEC treatment for selective CH<sub>3</sub>OH oxidation into HCHO. The surface fluorination simultaneously improved the reaction kinetics and selectivity for HCHO synthesis on BiVO<sub>4</sub> photoanode, where the formation of metal‒F bonds promoted the CH<sub>3</sub>OH molecules adsorption, O‒H bond stretching, C‒H bond activation, and eventually HCHO desorption, resulting in excellent HCHO production with high selectivity. The optimal photoanode BVO-F2 obtained a photocurrent density of 3.24 mA cm<sup>−2</sup> at 1.2 V<sub>RHE</sub>, which is about twice that of the bulk BVO photoanode (1.66 mA cm<sup>−2</sup>). In addition, at 0.8V<sub>RHE</sub>, the Faraday efficiency of BVO-F2 PEC CH<sub>3</sub>OH oxidation for HCHO synthesis reached 90.7%, and maintained relatively stable performance in continuous oxidation for 5 h, and finally accumulated 98.12 µmol HCHO. This work illustrates the potential of surface functionalization in PEC conversion of small molecules, as well as in regulating charge dynamics and catalytic reaction thermodynamics.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 227-236"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64857-1
Xinyi Ma , Ziyi Xiao , Xueqing Hu , Haobin Hu , Wenhua Xue , Enzhou Liu
Developing sustainable, low-cost H2S conversion technologies holds significant importance for the coal chemical and petrochemical industries. Herein, twinned Cd0.5Zn0.5S (T-CZS) homojunctions serve as model photocatalysts, with a Na2S/NaH2PO2 solution simulating H2S absorption to regulate S2−/HS− transformation pathways for concurrent efficient H2 evolution and desulfurization. Notably, at 3 mol∙L−1 NaH2PO2 concentration, the H2 evolution rate (rH2) over T-CZS reaches 233.9 mmol∙g−1∙h−1—representing a 5.5-fold enhancement versus 0.1 mol∙L−1 Na2S alone. Mechanistic studies reveal that the two-step oxidation of H2PO2− delivers four electrons for H+ reduction while simultaneously scavenging deleterious S22− species. This dual function mitigates light-absorption competition, enhances interfacial electron density, and accelerates H2-evolution kinetics. Further, Co3(PO4)2/CoSx loading boosts H2 production to 292.1 mmol∙g−1∙h−1, primarily ascribed to suppressed bulk/interface charge recombination. Crucially, acidification of post-reaction solutions yields pure elemental sulfur (S) as a yellow solid. Practical viability was validated using H2S preparation and absorption system, confirming robust catalyst performance and system efficacy for integrated high-efficiency H2 production and S recovery. The critical role and significant potential of H2PO2− in enhancing H2 evolution in S2−/HS− solutions were emphasized, offering potential strategies for efficient photocatalytic conversion of S2−/HS−. This work establishes a new paradigm for green, economical H2S valorization.
{"title":"Synergetic photocatalytic H2 evolution and H2S conversion over S-scheme Co3(PO4)2/CoSx/twinned-Cd0.5Zn0.5S","authors":"Xinyi Ma , Ziyi Xiao , Xueqing Hu , Haobin Hu , Wenhua Xue , Enzhou Liu","doi":"10.1016/S1872-2067(25)64857-1","DOIUrl":"10.1016/S1872-2067(25)64857-1","url":null,"abstract":"<div><div>Developing sustainable, low-cost H<sub>2</sub>S conversion technologies holds significant importance for the coal chemical and petrochemical industries. Herein, twinned Cd<sub>0.5</sub>Zn<sub>0.5</sub>S (T-CZS) homojunctions serve as model photocatalysts, with a Na<sub>2</sub>S/NaH<sub>2</sub>PO<sub>2</sub> solution simulating H<sub>2</sub>S absorption to regulate S<sup>2−</sup>/HS<sup>−</sup> transformation pathways for concurrent efficient H<sub>2</sub> evolution and desulfurization. Notably, at 3 mol∙L<sup>−1</sup> NaH<sub>2</sub>PO<sub>2</sub> concentration, the H<sub>2</sub> evolution rate (<em>r</em><sub>H2</sub>) over T-CZS reaches 233.9 mmol∙g<sup>−1</sup>∙h<sup>−1</sup>—representing a 5.5-fold enhancement versus 0.1 mol∙L<sup>−1</sup> Na<sub>2</sub>S alone. Mechanistic studies reveal that the two-step oxidation of H<sub>2</sub>PO<sub>2</sub><sup>−</sup> delivers four electrons for H<sup>+</sup> reduction while simultaneously scavenging deleterious S<sub>2</sub><sup>2−</sup> species. This dual function mitigates light-absorption competition, enhances interfacial electron density, and accelerates H<sub>2</sub>-evolution kinetics. Further, Co<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>/CoS<sub><em>x</em></sub> loading boosts H<sub>2</sub> production to 292.1 mmol∙g<sup>−1</sup>∙h<sup>−1</sup>, primarily ascribed to suppressed bulk/interface charge recombination. Crucially, acidification of post-reaction solutions yields pure elemental sulfur (S) as a yellow solid. Practical viability was validated using H<sub>2</sub>S preparation and absorption system, confirming robust catalyst performance and system efficacy for integrated high-efficiency H<sub>2</sub> production and S recovery. The critical role and significant potential of H<sub>2</sub>PO<sub>2</sub><sup>−</sup> in enhancing H<sub>2</sub> evolution in S<sup>2−</sup>/HS<sup>−</sup> solutions were emphasized, offering potential strategies for efficient photocatalytic conversion of S<sup>2−</sup>/HS<sup>−</sup>. This work establishes a new paradigm for green, economical H<sub>2</sub>S valorization.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 146-158"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64878-9
Xue Bai , Tianmi Tang , Jingru Sun , Fuquan Bai , Jing Hu , Jingqi Guan
Heterometallic doping can modulate the electron distribution of a catalyst, thereby influencing its intrinsic activity. In this study, we pioneer zinc doping within copper hydroxy oxides (CuOxHy) to alter the electronic structure and geometry, unlocking a distinct proton-coupled dynamic catalysis mechanism and significantly improving electrochemical CO2 reduction reaction (CO2RR) pathway selectivity toward formate. The Cu0.4Zn0.6OxHy catalyst, synthesized via a template co-precipitation method, exhibits a 4.1-fold enhancement of Faraday efficiency of formate over pristine CuOxHy at ‒1.1 V vs. RHE. In-situ Raman and X-ray photoelectron spectroscopy results confirm that the Cu0.4Zn0.6OxHy catalyst undergoes surface electron reconfiguration while maintaining bulk structural integrity with sustained Cu redox cycling, preserving the key active sites that sustain performance during CO2RR. Density functional theory calculations show that Zn doping effectively modulates the d-band center of Cu, enhances interfacial charge transfer with the *HCOO adsorbate, and lowers the energy barrier of the limiting step (CO2 → *HCOO), thereby boosting CO2RR performance. This work establishes a design principle for modulating the electronic structure of Cu-based hydroxides by zinc doping, highlighting dopant-induced electronic redistribution as a critical factor for achieving high formate selectivity.
{"title":"Engineering d-band structure of Zn-doped CuOxHy for boosting CO2 electroreduction performance","authors":"Xue Bai , Tianmi Tang , Jingru Sun , Fuquan Bai , Jing Hu , Jingqi Guan","doi":"10.1016/S1872-2067(25)64878-9","DOIUrl":"10.1016/S1872-2067(25)64878-9","url":null,"abstract":"<div><div>Heterometallic doping can modulate the electron distribution of a catalyst, thereby influencing its intrinsic activity. In this study, we pioneer zinc doping within copper hydroxy oxides (CuO<sub><em>x</em></sub>H<sub><em>y</em></sub>) to alter the electronic structure and geometry, unlocking a distinct proton-coupled dynamic catalysis mechanism and significantly improving electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) pathway selectivity toward formate. The Cu<sub>0.4</sub>Zn<sub>0.6</sub>O<sub><em>x</em></sub>H<sub><em>y</em></sub> catalyst, synthesized via a template co-precipitation method, exhibits a 4.1-fold enhancement of Faraday efficiency of formate over pristine CuO<sub><em>x</em></sub>H<sub><em>y</em></sub> at ‒1.1 V <em>vs.</em> RHE. <em>In-situ</em> Raman and X-ray photoelectron spectroscopy results confirm that the Cu<sub>0.4</sub>Zn<sub>0.6</sub>O<sub><em>x</em></sub>H<sub><em>y</em></sub> catalyst undergoes surface electron reconfiguration while maintaining bulk structural integrity with sustained Cu redox cycling, preserving the key active sites that sustain performance during CO<sub>2</sub>RR. Density functional theory calculations show that Zn doping effectively modulates the <em>d</em>-band center of Cu, enhances interfacial charge transfer with the *HCOO adsorbate, and lowers the energy barrier of the limiting step (CO<sub>2</sub> → *HCOO), thereby boosting CO<sub>2</sub>RR performance. This work establishes a design principle for modulating the electronic structure of Cu-based hydroxides by zinc doping, highlighting dopant-induced electronic redistribution as a critical factor for achieving high formate selectivity.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 248-257"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-01Epub Date: 2026-01-08DOI: 10.1016/S1872-2067(25)64882-0
Yana Men , Yuzhou Jiao , Yanxing Zheng , Xiaoyan Wang , Shengli Chen , Peng Li
Protic ionic liquid (IL) modification has been demonstrated to be a promising approach for improving the oxygen reduction reaction (ORR) activity and electrochemical stability of catalysts. However, its fundamental mechanism remains largely elusive and controversial, and the possible roles of electrocatalytic interface microenvironment has been ignored so far. Herein, taking the well-structured iron phthalocyanine (FePc) as a model catalyst, it is found that the ORR activity evolution behavior induced by the protic IL modification exhibits a striking pH-dependence, that is, ORR is promoted in acid while slightly inhibited in alkaline. Integrating the electrokinetic analyses, ab initio molecular dynamics simulation and in situ surface-enhanced infrared absorption spectroscopy, we show that the discrepancy in activity evolution arises from the regulation of IL modification on the vastly dissimilar electrochemical interfacial structures under acid and alkaline ORR conditions. Such mechanistic picture can be further supported by the fact that the protic IL with a lower pKa renders a higher acid ORR activity. This study provides a unique interfacial perspective for understanding the IL modifiers-modulated ORR performance and highlights opportunities for developing cost-effective and high-efficiency proton exchange membrane fuel cells through the functional modulation of electrocatalytic interfaces.
{"title":"pH-dependent protic ionic liquid tuning effect on oxygen reduction activity of a molecular iron catalyst and its electrochemical interfacial origin","authors":"Yana Men , Yuzhou Jiao , Yanxing Zheng , Xiaoyan Wang , Shengli Chen , Peng Li","doi":"10.1016/S1872-2067(25)64882-0","DOIUrl":"10.1016/S1872-2067(25)64882-0","url":null,"abstract":"<div><div>Protic ionic liquid (IL) modification has been demonstrated to be a promising approach for improving the oxygen reduction reaction (ORR) activity and electrochemical stability of catalysts. However, its fundamental mechanism remains largely elusive and controversial, and the possible roles of electrocatalytic interface microenvironment has been ignored so far. Herein, taking the well-structured iron phthalocyanine (FePc) as a model catalyst, it is found that the ORR activity evolution behavior induced by the protic IL modification exhibits a striking pH-dependence, that is, ORR is promoted in acid while slightly inhibited in alkaline. Integrating the electrokinetic analyses, ab initio molecular dynamics simulation and in situ surface-enhanced infrared absorption spectroscopy, we show that the discrepancy in activity evolution arises from the regulation of IL modification on the vastly dissimilar electrochemical interfacial structures under acid and alkaline ORR conditions. Such mechanistic picture can be further supported by the fact that the protic IL with a lower p<em>K</em><sub>a</sub> renders a higher acid ORR activity. This study provides a unique interfacial perspective for understanding the IL modifiers-modulated ORR performance and highlights opportunities for developing cost-effective and high-efficiency proton exchange membrane fuel cells through the functional modulation of electrocatalytic interfaces.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 258-269"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochemical synthesis of amides from carbon- and nitrogen-containing small molecules is alluring from the view of carbon neutrality. Previous works were mainly focused on electro-reduction coupling of C–N bond to prepare amides coupled with the useless oxygen evolution reaction on the anode. But, the competing hydrogen evolution reaction is more favorable in dynamics on the cathode, severely retarding the Faradaic efficiency of the amides. Very recently, electro-oxidation construction of C–N bond via coupling the cheap C- and N-containing small molecules to achieve high energy efficiency emerges as a rising star, while the big challenge lies in preventing the sole oxidation of feedstocks. In this perspective, we highlight the recent progress in anodic electro-oxidation synthesis of amides and the potential reaction mechanism. We also discuss the application potential and the development opportunities of the electro-oxidation strategy for amides synthesis from carbon- and nitrogen-containing small molecules.
{"title":"Electro-oxidation synthesis of amides from carbon- and nitrogen-containing small molecules","authors":"Aijing Ma , Baian Shen , Minghao Guo , Chengying Guo , Yifu Yu","doi":"10.1016/S1872-2067(25)64855-8","DOIUrl":"10.1016/S1872-2067(25)64855-8","url":null,"abstract":"<div><div>Electrochemical synthesis of amides from carbon- and nitrogen-containing small molecules is alluring from the view of carbon neutrality. Previous works were mainly focused on electro-reduction coupling of C–N bond to prepare amides coupled with the useless oxygen evolution reaction on the anode. But, the competing hydrogen evolution reaction is more favorable in dynamics on the cathode, severely retarding the Faradaic efficiency of the amides. Very recently, electro-oxidation construction of C–N bond via coupling the cheap C- and N-containing small molecules to achieve high energy efficiency emerges as a rising star, while the big challenge lies in preventing the sole oxidation of feedstocks. In this perspective, we highlight the recent progress in anodic electro-oxidation synthesis of amides and the potential reaction mechanism. We also discuss the application potential and the development opportunities of the electro-oxidation strategy for amides synthesis from carbon- and nitrogen-containing small molecules.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 1-6"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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