Pub Date : 2026-01-21DOI: 10.1016/j.mcat.2026.115721
Sicheng Hu , Baoying Liang , Yiming Tang
Perylene diimide (PDI) is an n-type organic semiconductor characterized by strong visible-light absorption and high stability, making it a promising candidate for photocatalytic reactions. Nevertheless, its efficacy is hindered by rapid charge recombination and a limited visible-light response. Recent advancements in molecular engineering and structural modification strategies, including bay-region modification, polymerization and heterojunction construction of PDI have been adopted to regulate their band structure, strengthen the built-in electric field, accelerate charge separation/migration, and extend the photoresponse range, thus boosting the photocatalytic performance. This review summarizes the progress made in PDI-based materials for pollutant degradation and related energy and environmental applications, with an emphasis on structure–activity relationships and catalytic mechanisms. Additionally, current challenges and future directions are discussed to inform the design of high-performance PDI photocatalysts.
{"title":"Perylene diimide photocatalysts: Structure-activity relationships and research progress in photocatalysis","authors":"Sicheng Hu , Baoying Liang , Yiming Tang","doi":"10.1016/j.mcat.2026.115721","DOIUrl":"10.1016/j.mcat.2026.115721","url":null,"abstract":"<div><div>Perylene diimide (PDI) is an n-type organic semiconductor characterized by strong visible-light absorption and high stability, making it a promising candidate for photocatalytic reactions. Nevertheless, its efficacy is hindered by rapid charge recombination and a limited visible-light response. Recent advancements in molecular engineering and structural modification strategies, including bay-region modification, polymerization and heterojunction construction of PDI have been adopted to regulate their band structure, strengthen the built-in electric field, accelerate charge separation/migration, and extend the photoresponse range, thus boosting the photocatalytic performance. This review summarizes the progress made in PDI-based materials for pollutant degradation and related energy and environmental applications, with an emphasis on structure–activity relationships and catalytic mechanisms. Additionally, current challenges and future directions are discussed to inform the design of high-performance PDI photocatalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115721"},"PeriodicalIF":4.9,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.mcat.2026.115733
Vanessa A. Pereira , Maria Inês Madeira , Rita Oliveira , Patrícia A Simões , F.A. Rocha , Jorge F.J. Coelho , Arménio C. Serra
The hydrogenation of colophony was explored for the first time by catalytic transfer hydrogenation using different hydrogen sources and Pd/C as the catalyst. Compared to conventional hydrogenation, which requires molecular hydrogen under high pressure, catalytic transfer hydrogenation uses a suitable H2-donor and requires simple operating conditions. In this study, different experimental conditions were tested to achieve optimal reaction conditions using raw industrial colophony as the substrate. The results showed that when sodium formate was used as a hydrogen donor, a high conversion of the original resin acids, such as abietic acid (AA) and its isomers (AA+) were achieved, producing high amount of a mixture of dihydroabietic acid (DIA). The hydrogenated colophony showed a lower glass transition temperature (Tg) than the starting material, (30.7 °C versus 49.2 °C). The Pd/C catalyst could be recycled and reused in consecutive hydrogenation reactions. The strategy for colophony hydrogenation presented herein is simple and can be much more favorable from a practical and economic point of view.
{"title":"Catalytic transfer hydrogenation of colophony","authors":"Vanessa A. Pereira , Maria Inês Madeira , Rita Oliveira , Patrícia A Simões , F.A. Rocha , Jorge F.J. Coelho , Arménio C. Serra","doi":"10.1016/j.mcat.2026.115733","DOIUrl":"10.1016/j.mcat.2026.115733","url":null,"abstract":"<div><div>The hydrogenation of colophony was explored for the first time by catalytic transfer hydrogenation using different hydrogen sources and Pd/C as the catalyst. Compared to conventional hydrogenation, which requires molecular hydrogen under high pressure, catalytic transfer hydrogenation uses a suitable H<sub>2</sub>-donor and requires simple operating conditions. In this study, different experimental conditions were tested to achieve optimal reaction conditions using raw industrial colophony as the substrate. The results showed that when sodium formate was used as a hydrogen donor, a high conversion of the original resin acids, such as abietic acid (AA) and its isomers (AA+) were achieved, producing high amount of a mixture of dihydroabietic acid (DIA). The hydrogenated colophony showed a lower glass transition temperature (T<sub>g</sub>) than the starting material, (30.7 °C versus 49.2 °C). The Pd/C catalyst could be recycled and reused in consecutive hydrogenation reactions. The strategy for colophony hydrogenation presented herein is simple and can be much more favorable from a practical and economic point of view.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115733"},"PeriodicalIF":4.9,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.mcat.2026.115739
Anshuang Wu , Chaofan Li , Longmei Shi , Shengyun Xu , Shucan Qin , Fei Yu , Yanrong Liu , Xiaomin Lu , Yunqian Ma , Jiaming Mao
Ni3+ (NiOOH) species are recognized as the principal active centers for the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to the high-value platform chemical 2,5-furandicarboxylic acid (FDCA) over Ni-based catalysts. However, the oxidation of Ni2+ to Ni3+ generally requires a high anodic potential, which competes with the oxygen evolution reaction (OER) and thereby diminishes catalytic efficiency. Herein, we report a facile one-step calcination strategy incorporating Li into the precursor, employing a deep eutectic solvent (DES, ChCl/urea) as a soft template to synthesize an octahedral Li-NiO/Ni@N electrocatalyst for efficient HMF electrooxidation. Experimental and density functional theory (DFT) analyses reveal that Li incorporation promotes the preferential formation and stabilization of Ni3+ species, which ensures early high current density (>20 mA cm-2) prior to the Ni2+/Ni3+ transition, thereby lowering the energetic barrier, preserving active sites, and steering selectivity by suppressing OER competition during HMF oxidation. The optimized catalyst achieves 97.8 % HMF conversion, 96.8 % FDCA yield, and 94.1 % Faradaic efficiency. Furthermore, the hydrogen-bond network in DES ensures homogeneous metal ion dispersion, while the octahedral architecture enhances metal site density and active-site exposure. The N-doped carbon layer improves surface hydrophilicity and corrosion resistance, further augmenting electrooxidation activity. This work highlights the dual synergy of Li doping and DES-mediated morphological control, providing mechanistic insights into Ni3+-driven HMF oxidation and a rational design strategy for high-performance Ni-based electrocatalysts.
{"title":"Deep eutectic solvent induced octahedral Li-NiO/Ni@N nanostructure: an efficient electrocatalyst for 5-hydroxymethylfurfural electrooxidation","authors":"Anshuang Wu , Chaofan Li , Longmei Shi , Shengyun Xu , Shucan Qin , Fei Yu , Yanrong Liu , Xiaomin Lu , Yunqian Ma , Jiaming Mao","doi":"10.1016/j.mcat.2026.115739","DOIUrl":"10.1016/j.mcat.2026.115739","url":null,"abstract":"<div><div>Ni<sup>3+</sup> (NiOOH) species are recognized as the principal active centers for the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to the high-value platform chemical 2,5-furandicarboxylic acid (FDCA) over Ni-based catalysts. However, the oxidation of Ni<sup>2+</sup> to Ni<sup>3+</sup> generally requires a high anodic potential, which competes with the oxygen evolution reaction (OER) and thereby diminishes catalytic efficiency. Herein, we report a facile one-step calcination strategy incorporating Li into the precursor, employing a deep eutectic solvent (DES, ChCl/urea) as a soft template to synthesize an octahedral Li-NiO/Ni@N electrocatalyst for efficient HMF electrooxidation. Experimental and density functional theory (DFT) analyses reveal that Li incorporation promotes the preferential formation and stabilization of Ni<sup>3+</sup> species, which ensures early high current density (>20 mA cm<sup>-2</sup>) prior to the Ni<sup>2+</sup>/Ni<sup>3+</sup> transition, thereby lowering the energetic barrier, preserving active sites, and steering selectivity by suppressing OER competition during HMF oxidation. The optimized catalyst achieves 97.8 % HMF conversion, 96.8 % FDCA yield, and 94.1 % Faradaic efficiency. Furthermore, the hydrogen-bond network in DES ensures homogeneous metal ion dispersion, while the octahedral architecture enhances metal site density and active-site exposure. The N-doped carbon layer improves surface hydrophilicity and corrosion resistance, further augmenting electrooxidation activity. This work highlights the dual synergy of Li doping and DES-mediated morphological control, providing mechanistic insights into Ni<sup>3+</sup>-driven HMF oxidation and a rational design strategy for high-performance Ni-based electrocatalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115739"},"PeriodicalIF":4.9,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-19DOI: 10.1016/j.mcat.2026.115731
Xin Zeng , Qiling Duan , Zhenxing Li , Xinyu Tan , Moyu Liao , Zhongxu Dai
In this study, we designed and constructed a cobalt-based oxide catalyst (CoOx) grown in situ on porous copper foam (CF-P). By modulating the phase composition of CoOx and the electronic structure of the CF-P support, efficient conversion of NO₃- and selective formation of NH₃ were achieved. The CF-P support not only provides a stable loading substrate and efficient electron transport pathways for the semi-crystalline CoOx active phase, but its porous surface structure also enhances nitrate adsorption, facilitating the deoxygenation step to form nitrite intermediates. The mixed-valence states (Co²⁺/Co³⁺) and oxygen vacancy defects in CoOx form a partially crystalline Co phase that promotes the generation and transfer of active hydrogen (H*), thereby efficiently facilitating the hydrogenation of nitrite-the rate-determining step. Through tandem catalysis between the two phases, highly efficient nitrate reduction is realized. Under optimal electrolysis conditions, the CoOx/CF-P catalyst achieves a Faradaic efficiency of 92.98 % for NH₃ with a production rate of 12.73 mg·h-1·cm-2. Moreover, after 10 hours of continuous operation, no significant decay in catalytic activity or selectivity was observed, demonstrating excellent stability. This performance is attributed to the synergistic tandem mechanism between dual active sites and the presence of oxygen vacancy defects. This work provides new insights into the design of highly efficient NO3RR catalysts and establishes a material foundation for low-cost, scalable electrocatalytic ammonia production.
{"title":"A semi-crystalline CoOx/CF-P tandem catalyst for the highly efficient reduction of nitrate to ammonia","authors":"Xin Zeng , Qiling Duan , Zhenxing Li , Xinyu Tan , Moyu Liao , Zhongxu Dai","doi":"10.1016/j.mcat.2026.115731","DOIUrl":"10.1016/j.mcat.2026.115731","url":null,"abstract":"<div><div>In this study, we designed and constructed a cobalt-based oxide catalyst (CoO<sub>x</sub>) grown in situ on porous copper foam (CF-P). By modulating the phase composition of CoO<sub>x</sub> and the electronic structure of the CF-P support, efficient conversion of NO₃<sup>-</sup> and selective formation of NH₃ were achieved. The CF-P support not only provides a stable loading substrate and efficient electron transport pathways for the semi-crystalline CoO<sub>x</sub> active phase, but its porous surface structure also enhances nitrate adsorption, facilitating the deoxygenation step to form nitrite intermediates. The mixed-valence states (Co²⁺/Co³⁺) and oxygen vacancy defects in CoO<sub>x</sub> form a partially crystalline Co phase that promotes the generation and transfer of active hydrogen (H*), thereby efficiently facilitating the hydrogenation of nitrite-the rate-determining step. Through tandem catalysis between the two phases, highly efficient nitrate reduction is realized. Under optimal electrolysis conditions, the CoO<sub>x</sub>/CF-P catalyst achieves a Faradaic efficiency of 92.98 % for NH₃ with a production rate of 12.73 mg·h<sup>-1</sup>·cm<sup>-2</sup>. Moreover, after 10 hours of continuous operation, no significant decay in catalytic activity or selectivity was observed, demonstrating excellent stability. This performance is attributed to the synergistic tandem mechanism between dual active sites and the presence of oxygen vacancy defects. This work provides new insights into the design of highly efficient NO<sub>3</sub>RR catalysts and establishes a material foundation for low-cost, scalable electrocatalytic ammonia production.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115731"},"PeriodicalIF":4.9,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-19DOI: 10.1016/j.mcat.2026.115737
Rekha Muthuvel, Renugadevi Chelladurai, Cindrella Louis
The ever-growing need for cobalt-containing perovskites with high catalytic ability in energy conversion and storage systems, such as batteries, and their frequent incompatibility due to their large thermal expansion coefficient with electrolyte material in devices such as solid oxide fuel cells (SOFCs), raises issues concerning their availability and cost in the future. However, Mn/Fe/Ni-containing perovskites, relative to cobalt-containing ones, combine high catalytic ability, sustainability, and affordability with superior resistance to geopolitical issues. Because of performance differences with traditional cobalt-based systems, Ni–Mn and Fe–Mn bimetallic perovskite oxide catalysts are still largely unexplored for oxygen evolution and oxygen reduction processes (OER/ORR) despite these benefits. In order to improve electrocatalytic activity and stability by interfacial engineering, conductive carbon nanosheets functionalised with phosphorus (CP) were used as supports for Ni/Fe/Mn perovskites. Together with the defect-rich active sites supplied by CP layers, the advantageous, e.g., occupancies of low-spin Ni³⁺ (eg¹) and high-spin Mn³⁺ (eg¹) in Ni0.2Fe0.8MnO3 (NFMO) synergistically increase OER/ORR activity in the logically constructed NFMO/CP composite.
{"title":"Cobalt-free perovskite catalyst coupled with phosphorous doped carbon nanosheets for oxygen electrocatalysis","authors":"Rekha Muthuvel, Renugadevi Chelladurai, Cindrella Louis","doi":"10.1016/j.mcat.2026.115737","DOIUrl":"10.1016/j.mcat.2026.115737","url":null,"abstract":"<div><div>The ever-growing need for cobalt-containing perovskites with high catalytic ability in energy conversion and storage systems, such as batteries, and their frequent incompatibility due to their large thermal expansion coefficient with electrolyte material in devices such as solid oxide fuel cells (SOFCs), raises issues concerning their availability and cost in the future. However, Mn/Fe/Ni-containing perovskites, relative to cobalt-containing ones, combine high catalytic ability, sustainability, and affordability with superior resistance to geopolitical issues. Because of performance differences with traditional cobalt-based systems, Ni–Mn and Fe–Mn bimetallic perovskite oxide catalysts are still largely unexplored for oxygen evolution and oxygen reduction processes (OER/ORR) despite these benefits. In order to improve electrocatalytic activity and stability by interfacial engineering, conductive carbon nanosheets functionalised with phosphorus (CP) were used as supports for Ni/Fe/Mn perovskites. Together with the defect-rich active sites supplied by CP layers, the advantageous, e.g., occupancies of low-spin Ni³⁺ (eg¹) and high-spin Mn³⁺ (eg¹) in Ni<sub>0.2</sub>Fe<sub>0.8</sub>MnO<sub>3</sub> (NFMO) synergistically increase OER/ORR activity in the logically constructed NFMO/CP composite.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115737"},"PeriodicalIF":4.9,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-17DOI: 10.1016/j.mcat.2026.115718
Tao Li , Zhenwu Jin , Yi Xu , Jiahua Zou , Ling-Ling Wang , Liang Xu
Photocatalytic water splitting is a promising approach for clean H₂ production, yet current materials often suffer from inefficient charge separation and narrow light absorption. Herein, we systematically investigate the photocatalytic performance of a Z-scheme MoSi₂N₄/GaO van der Waals heterostructure via first-principles calculations. The results reveal that the heterostructure exhibits an ideal Z-scheme band alignment, enabling spatial separation of photogenerated electrons (in MoSi₂N₄) and holes (in GaO). Charge density difference and electrostatic potential analyses confirm an internal electric field directing electron transfer from MoSi₂N₄ to GaO, enhancing interfacial charge transport. Free energy calculations demonstrate low overpotentials for both hydrogen evolution (HER, 0.43 eV) and oxygen evolution reactions (OER), indicating excellent catalytic activity. Notably, the heterostructure shows strong visible-to-near-infrared light absorption and achieves a high solar-to-hydrogen (STH) efficiency of 27.03%, surpassing the 10% threshold for practical applications. These findings highlight the MoSi₂N₄/GaO heterostructure as a promising photocatalyst for efficient solar-driven water splitting.
{"title":"Z-Scheme MoSi₂N₄/GaO van der waals heterostructure for efficient photocatalytic water splitting","authors":"Tao Li , Zhenwu Jin , Yi Xu , Jiahua Zou , Ling-Ling Wang , Liang Xu","doi":"10.1016/j.mcat.2026.115718","DOIUrl":"10.1016/j.mcat.2026.115718","url":null,"abstract":"<div><div>Photocatalytic water splitting is a promising approach for clean H₂ production, yet current materials often suffer from inefficient charge separation and narrow light absorption. Herein, we systematically investigate the photocatalytic performance of a Z-scheme MoSi₂N₄/GaO van der Waals heterostructure via first-principles calculations. The results reveal that the heterostructure exhibits an ideal Z-scheme band alignment, enabling spatial separation of photogenerated electrons (in MoSi₂N₄) and holes (in GaO). Charge density difference and electrostatic potential analyses confirm an internal electric field directing electron transfer from MoSi₂N₄ to GaO, enhancing interfacial charge transport. Free energy calculations demonstrate low overpotentials for both hydrogen evolution (HER, 0.43 eV) and oxygen evolution reactions (OER), indicating excellent catalytic activity. Notably, the heterostructure shows strong visible-to-near-infrared light absorption and achieves a high solar-to-hydrogen (STH) efficiency of 27.03%, surpassing the 10% threshold for practical applications. These findings highlight the MoSi₂N₄/GaO heterostructure as a promising photocatalyst for efficient solar-driven water splitting.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115718"},"PeriodicalIF":4.9,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1016/j.mcat.2026.115720
Zandong Zhang , Chen Lei , ChenYu Xia , Xiaoyan Wang , Zhihui Jiang , Yang Qu , Dan Li , Xin Qu , Jingsong Li , Jie Wang , Jimmy Yun , Jie Zhang , Hong Zhao , Zuobo Yang
The development of non-precious metal electrocatalysts for the hydrogen evolution reaction (HER) that combine high activity, durability, and cost-effectiveness for industrial alkaline water electrolysis remains a significant challenge. Herein, we report a Ni-W-Zn ternary alloy electrode engineered through a synergistic strategy of composition optimization and surface reconstruction. A fine-grained Ni-W-Zn alloy was first prepared by controlled electrodeposition. Subsequent electrochemical etching selectively dissolved Zn and modulated the oxidation states of Ni and W, simultaneously constructing a three-dimensional (3D) porous network structure on the electrode surface. This strategy simultaneously reduced internal stress, suppressed the hydrogen evolution side reaction during electrodeposition, and mitigated hydrogen embrittlement during the preparation process, thereby significantly mitigating hydrogen embrittlement during the preparation process by forming a denser coating that acts as a barrier against hydrogen penetration. This unique architecture significantly increased the electrochemical surface area and exposed more active sites. The optimized electrode exhibited exceptional HER performance in 1.0 M KOH, requiring low overpotentials of only 18.0 mV and 215.1 mV to achieve current densities of 10 mA cm⁻² and 500 mA cm⁻², respectively. Furthermore, it demonstrated outstanding long-term stability, showing negligible performance degradation over 200 h of continuous operation at 500 mA cm⁻². When employed as a cathode in an alkaline electrolyzer, the cell voltage was only 1.688 V at 100 mA cm⁻². After a 200-hour stability test, the voltage increase rate was only 0.24 mV/h, demonstrating good durability. This work highlights electrochemical etching as a powerful post-treatment technique for fabricating high-performance, stable HER electrodes, offering a promising avenue for large-scale hydrogen production.
开发具有高活性、耐用性和成本效益的工业碱水电解析氢反应（HER）用非贵金属电催化剂仍然是一个重大挑战。在此，我们报告了一种通过成分优化和表面重建协同策略设计的Ni-W-Zn三元合金电极。采用可控电沉积法制备了一种细晶Ni-W-Zn合金。随后的电化学蚀刻选择性地溶解Zn并调制Ni和W的氧化态，同时在电极表面构建三维（3D）多孔网络结构。该策略同时降低了内应力，抑制了电沉积过程中的析氢副反应，减轻了制备过程中的氢脆，从而通过形成更致密的涂层来防止氢渗透，从而显著减轻了制备过程中的氢脆。这种独特的结构显著增加了电化学表面积，暴露了更多的活性位点。优化后的电极在1.0 M KOH条件下表现出优异的HER性能，仅需要18.0 mV和215.1 mV的低过电位就可以分别达到10 mA cm⁻²和500 mA cm⁻²的电流密度。此外，它表现出了出色的长期稳定性，在500毫安厘米（⁻²）下连续工作200小时，性能下降可以忽略不计。当在碱性电解槽中用作阴极时，该电池在100毫安厘米（⁻²）时的电压仅为1.688 V。经过200小时的稳定性试验，电压增幅仅为0.24 mV/h，具有良好的耐久性。这项工作强调了电化学蚀刻作为一种强大的后处理技术，可以制造高性能、稳定的HER电极，为大规模制氢提供了一条有前途的途径。
{"title":"Etching-reconstruction enhanced Ni-W-Zn ternary alloy hydrogen evolution reaction electrode","authors":"Zandong Zhang , Chen Lei , ChenYu Xia , Xiaoyan Wang , Zhihui Jiang , Yang Qu , Dan Li , Xin Qu , Jingsong Li , Jie Wang , Jimmy Yun , Jie Zhang , Hong Zhao , Zuobo Yang","doi":"10.1016/j.mcat.2026.115720","DOIUrl":"10.1016/j.mcat.2026.115720","url":null,"abstract":"<div><div>The development of non-precious metal electrocatalysts for the hydrogen evolution reaction (HER) that combine high activity, durability, and cost-effectiveness for industrial alkaline water electrolysis remains a significant challenge. Herein, we report a Ni-W-Zn ternary alloy electrode engineered through a synergistic strategy of composition optimization and surface reconstruction. A fine-grained Ni-W-Zn alloy was first prepared by controlled electrodeposition. Subsequent electrochemical etching selectively dissolved Zn and modulated the oxidation states of Ni and W, simultaneously constructing a three-dimensional (3D) porous network structure on the electrode surface. This strategy simultaneously reduced internal stress, suppressed the hydrogen evolution side reaction during electrodeposition, and mitigated hydrogen embrittlement during the preparation process, thereby significantly mitigating hydrogen embrittlement during the preparation process by forming a denser coating that acts as a barrier against hydrogen penetration. This unique architecture significantly increased the electrochemical surface area and exposed more active sites. The optimized electrode exhibited exceptional HER performance in 1.0 M KOH, requiring low overpotentials of only 18.0 mV and 215.1 mV to achieve current densities of 10 mA cm⁻² and 500 mA cm⁻², respectively. Furthermore, it demonstrated outstanding long-term stability, showing negligible performance degradation over 200 h of continuous operation at 500 mA cm⁻². When employed as a cathode in an alkaline electrolyzer, the cell voltage was only 1.688 V at 100 mA cm⁻². After a 200-hour stability test, the voltage increase rate was only 0.24 mV/h, demonstrating good durability. This work highlights electrochemical etching as a powerful post-treatment technique for fabricating high-performance, stable HER electrodes, offering a promising avenue for large-scale hydrogen production.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115720"},"PeriodicalIF":4.9,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1016/j.mcat.2026.115730
Mingsheng Luo , Xiaoteng Cui , Yuanyuan Fang , Changke Shao , Roshni Rahman , Lingxin Chen , Hao Sun , Minwei Yi , Yutong Liu , Yiduo Huo , Zihan Xu
CO2-to-methanol is a promising process for carbon utilization to produce sustainable fuel and chemicals. Catalytic performance of Cu-based Layered Double Hydroxide (LDH)-derived catalysts for CO2 hydrogenation to produce methanol was investigated in this work. Various secondary metallic components, Al, Ga, Cr, In, Sm and La were employed to prepare a series of Me-Cu/LDH type of catalyst for CO2-to-methanol reaction. The catalysts were synthesized using a co-precipitation method, followed by calcination and reduction activation. Impact of the secondary metals on the structure of the prepared catalyst and their reaction performance was studied in fixed-bed reactor. The CO₂ hydrogenation activity and methanol selectivity of the prepared LDO catalyst were evaluated at 3.0 MPa and a gas hourly space velocity (GHSV) of 3.6 L·g⁻¹·h⁻¹, using a CO₂/H₂ ratio of 3. Synthesis conditions, including temperature and aging time, significantly affected the catalyst structural properties and catalytic performance. The results showed that the CuAl catalyst yielded the highest CO2 conversion up to 20%, while the CuIn catalyst generated the highest methanol selectivity above 74%. It can be reasonably proposed that the highly dispersed copper active sites in the CuAl catalyts contributed to the improved CO2 conversion, whereas the high concentration of oxygen vacancies in the CuIn catalyst promoted methanol formation. Furthermore, these catalysts showed good stability with no noticeable carbon deposition. These findings highlight the potential of LDH-based catalysts in CO2 hydrogenation and provide valuable insights for optimizing their structure and composition to enhance catalytic efficiency.
{"title":"Influence of the secondary metals on structure of the Cu/LDH catalyst for carbon dioxide-to-methanol reaction","authors":"Mingsheng Luo , Xiaoteng Cui , Yuanyuan Fang , Changke Shao , Roshni Rahman , Lingxin Chen , Hao Sun , Minwei Yi , Yutong Liu , Yiduo Huo , Zihan Xu","doi":"10.1016/j.mcat.2026.115730","DOIUrl":"10.1016/j.mcat.2026.115730","url":null,"abstract":"<div><div>CO<sub>2</sub>-to-methanol is a promising process for carbon utilization to produce sustainable fuel and chemicals. Catalytic performance of Cu-based Layered Double Hydroxide (LDH)-derived catalysts for CO<sub>2</sub> hydrogenation to produce methanol was investigated in this work. Various secondary metallic components, Al, Ga, Cr, In, Sm and La were employed to prepare a series of Me-Cu/LDH type of catalyst for CO<sub>2</sub>-to-methanol reaction. The catalysts were synthesized using a co-precipitation method, followed by calcination and reduction activation. Impact of the secondary metals on the structure of the prepared catalyst and their reaction performance was studied in fixed-bed reactor. The CO₂ hydrogenation activity and methanol selectivity of the prepared LDO catalyst were evaluated at 3.0 MPa and a gas hourly space velocity (GHSV) of 3.6 L·g⁻¹·h⁻¹, using a CO₂/H₂ ratio of 3. Synthesis conditions, including temperature and aging time, significantly affected the catalyst structural properties and catalytic performance. The results showed that the CuAl catalyst yielded the highest CO<sub>2</sub> conversion up to 20%, while the CuIn catalyst generated the highest methanol selectivity above 74%. It can be reasonably proposed that the highly dispersed copper active sites in the CuAl catalyts contributed to the improved CO<sub>2</sub> conversion, whereas the high concentration of oxygen vacancies in the CuIn catalyst promoted methanol formation. Furthermore, these catalysts showed good stability with no noticeable carbon deposition. These findings highlight the potential of LDH-based catalysts in CO<sub>2</sub> hydrogenation and provide valuable insights for optimizing their structure and composition to enhance catalytic efficiency.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115730"},"PeriodicalIF":4.9,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The catalytic activity of palladium nanoparticle (PdNPs) catalysts prepared using commonly known supports such as zeolite, MCM-41, graphene, and activated carbon was investigated for hydrogen generation from formic acid. As the result, the PdNPs supported activated carbon catalyst showed extremely high activity. To further investigate its function as a support, PdNPs supported catalysts using various activated carbons were prepared and their characterization, activities, and durability in hydrogen generation from formic acid were investigated in detail. Among them, the catalyst using activated carbon derived from coconut shell as a support showed the highest activity. The pores, surface area and three dimensional structure of activated carbon promote high dispersion of PdNPs and improve catalytic efficiency. It was also suggested that acidic functional groups have a positive effect on catalytic activity. Furthermore, the results of metal surface area and average Pd particle size using the CO pulse method showed a positive linear correlation between metal surface area and turnover frequency (TOF). It was found that PdNPs with metal surface area greater than 7.5 m2·g−1 and average Pd particle size <3.5 nm showed high activity. XPS measurement suggested that electron transfer occurred from PdNPs to supported carbon in the catalyst. Thus, PdNPs catalysts using activated carbon are promising catalyst supports for future industrial applications due to their high activity and excellent durability.
{"title":"Selection of activated carbon as a support in the preparation of facile highly active catalysts for hydrogen generation from formic acid","authors":"Nobuko Tsumori , Takeshi Toshima , Yukiko Shinozaki , Saori Takamatsu , Tomohiro Fukuda","doi":"10.1016/j.mcat.2026.115717","DOIUrl":"10.1016/j.mcat.2026.115717","url":null,"abstract":"<div><div>The catalytic activity of palladium nanoparticle (PdNPs) catalysts prepared using commonly known supports such as zeolite, MCM-41, graphene, and activated carbon was investigated for hydrogen generation from formic acid. As the result, the PdNPs supported activated carbon catalyst showed extremely high activity. To further investigate its function as a support, PdNPs supported catalysts using various activated carbons were prepared and their characterization, activities, and durability in hydrogen generation from formic acid were investigated in detail. Among them, the catalyst using activated carbon derived from coconut shell as a support showed the highest activity. The pores, surface area and three dimensional structure of activated carbon promote high dispersion of PdNPs and improve catalytic efficiency. It was also suggested that acidic functional groups have a positive effect on catalytic activity. Furthermore, the results of metal surface area and average Pd particle size using the CO pulse method showed a positive linear correlation between metal surface area and turnover frequency (TOF). It was found that PdNPs with metal surface area greater than 7.5 m<sup>2</sup>·g<sup>−1</sup> and average Pd particle size <3.5 nm showed high activity. XPS measurement suggested that electron transfer occurred from PdNPs to supported carbon in the catalyst. Thus, PdNPs catalysts using activated carbon are promising catalyst supports for future industrial applications due to their high activity and excellent durability.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115717"},"PeriodicalIF":4.9,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Silica derived from bagasse bottom ash significantly enhances the catalytic activity and stability of Ce, Mg, and Mg-Ce-oxide-supported nickel catalysts in CH4 and CO2 reforming reactions. In this work, silica-modified MgO- and CeO2-supported nickel catalysts were prepared by co-precipitation using bagasse-derived sodium silicate. Their catalytic performance for syngas production was subsequently evaluated in a packed-bed reactor under reforming conditions at 700°C. Among these, nickel catalyst supported on silica-modified MgO and CeO2 (Ni-MCS) exhibited superior CH4 and CO2 conversions and a more favorable H2/CO product ratio compared to nickel catalysts supported on pure silica or unmodified MgO-CeO2. This enhanced performance was attributed to the incorporation of Ce and/or Mg into the silica structure, which strengthened metal–support interactions, promoted the formation of stable Ni–Mg–O solid solutions and improved nickel dispersion on the silica-modified Mg-Ce-oxide support. In the SiO2-modified MgO-CeO2 support, various oxygen species—including lattice oxygen, surface-adsorbed oxygen, and surface hydroxyl groups or chemisorbed oxygen—were observed on the catalyst surface. Notably, a higher ratio of surface-adsorbed to lattice oxygen was detected, which plays a crucial role in the rapid oxidation of carbonaceous intermediates and effectively suppressed carbon deposition. Additionally, the increased medium-strength basic sites enhanced CO2 adsorption and dissociation, promoting CO formation and supporting carbon removal during the reaction.
{"title":"Silica-anchored cerium-magnesium supported nickel toward improved CO2 reforming of CH4","authors":"Pongsaporn Poosri , Orrakanya Phichairatanaphong , Thongthai Witoon , Metta Chareonpanich , Waleeporn Donphai","doi":"10.1016/j.mcat.2026.115722","DOIUrl":"10.1016/j.mcat.2026.115722","url":null,"abstract":"<div><div>Silica derived from bagasse bottom ash significantly enhances the catalytic activity and stability of Ce, Mg, and Mg-Ce-oxide-supported nickel catalysts in CH<sub>4</sub> and CO<sub>2</sub> reforming reactions. In this work, silica-modified MgO- and CeO<sub>2</sub>-supported nickel catalysts were prepared by co-precipitation using bagasse-derived sodium silicate. Their catalytic performance for syngas production was subsequently evaluated in a packed-bed reactor under reforming conditions at 700°C. Among these, nickel catalyst supported on silica-modified MgO and CeO<sub>2</sub> (Ni-MCS) exhibited superior CH<sub>4</sub> and CO<sub>2</sub> conversions and a more favorable H<sub>2</sub>/CO product ratio compared to nickel catalysts supported on pure silica or unmodified MgO-CeO<sub>2</sub>. This enhanced performance was attributed to the incorporation of Ce and/or Mg into the silica structure, which strengthened metal–support interactions, promoted the formation of stable Ni–Mg–O solid solutions and improved nickel dispersion on the silica-modified Mg-Ce-oxide support. In the SiO<sub>2</sub>-modified MgO-CeO<sub>2</sub> support, various oxygen species—including lattice oxygen, surface-adsorbed oxygen, and surface hydroxyl groups or chemisorbed oxygen—were observed on the catalyst surface. Notably, a higher ratio of surface-adsorbed to lattice oxygen was detected, which plays a crucial role in the rapid oxidation of carbonaceous intermediates and effectively suppressed carbon deposition. Additionally, the increased medium-strength basic sites enhanced CO<sub>2</sub> adsorption and dissociation, promoting CO formation and supporting carbon removal during the reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115722"},"PeriodicalIF":4.9,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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