Pub Date : 2026-01-20DOI: 10.1016/j.jcat.2026.116708
Xiaoqian Bai , Jialong Lin , Bingxue Cheng , Chunqi Yang , Xinlin Wang , Yuhang Li , Tamao Ishida , Toru Murayama , Guangli Xiu , Mingyue Lin
Ethylene glycol (EG), a primary byproduct from the alkaline hydrolysis of polyethylene terephthalate (PET), can serve as an alternative anode reaction to the oxygen evolution reaction (OER). This substitution significantly lowers the energy required for hydrogen production via water electrolysis. In this study, Fe(0.3 wt%)-CoPO was in situ synthesized on nickel foam (NF), showing great electrocatalytic activity. At just 1.426 V (vs. RHE), it achieves a current density of 100 mA cm−2 and a Faraday efficiency (FE) of 100%. At the 100 mA cm−2, the potential of the ethylene glycol oxidation reaction (EGOR) was 224 mV lower than that of OER, thereby reducing the total working potential and consequently lowering the energy consumption for hydrogen production at the cathode. In situ Raman spectroscopy further reveals that the high activity of EGOR is due to the generation of CoOOH species during the electrochemical reconstruction. Additionally, Fe incorporation has the effect of inhibiting the overoxidation of Co3+. This study successfully couples EGOR electrocatalysis with the production of valuable chemicals and hydrogen, providing new insights into high-performance EGOR catalytic systems.
乙二醇（EG）是聚对苯二甲酸乙二醇酯（PET）碱性水解的主要副产物，可以作为析氧反应（OER）的备选阳极反应。这种替代显著降低了通过水电解制氢所需的能量。本研究在泡沫镍（NF）上原位合成了Fe(0.3 wt%)-CoPO，表现出良好的电催化活性。在1.426 V （vs. RHE）下，它实现了100 mA cm−2的电流密度和100%的法拉第效率（FE）。在100 mA cm−2下，乙二醇氧化反应（EGOR）的电位比OER的电位低224 mV，从而降低了总工作电位，从而降低了阴极制氢的能耗。原位拉曼光谱进一步揭示了EGOR的高活性是由于电化学重构过程中CoOOH物质的生成。此外，铁的掺入还具有抑制Co3+过氧化的作用。该研究成功地将EGOR电催化与有价化学品和氢气的生产结合起来，为高性能EGOR催化系统提供了新的见解。
{"title":"Fe-induced Co (IV) elimination enhancing selective ethylene glycol oxidation at high current density","authors":"Xiaoqian Bai , Jialong Lin , Bingxue Cheng , Chunqi Yang , Xinlin Wang , Yuhang Li , Tamao Ishida , Toru Murayama , Guangli Xiu , Mingyue Lin","doi":"10.1016/j.jcat.2026.116708","DOIUrl":"10.1016/j.jcat.2026.116708","url":null,"abstract":"<div><div>Ethylene glycol (EG), a primary byproduct from the alkaline hydrolysis of polyethylene terephthalate (PET), can serve as an alternative anode reaction to the oxygen evolution reaction (OER). This substitution significantly lowers the energy required for hydrogen production via water electrolysis. In this study, Fe(0.3 wt%)-CoPO was <em>in situ</em> synthesized on nickel foam (NF), showing great electrocatalytic activity. At just 1.426 V (<em>vs.</em> RHE), it achieves a current density of 100 mA cm<sup>−2</sup> and a Faraday efficiency (FE) of 100%. At the 100 mA cm<sup>−2</sup>, the potential of the ethylene glycol oxidation reaction (EGOR) was 224 mV lower than that of OER, thereby reducing the total working potential and consequently lowering the energy consumption for hydrogen production at the cathode. <em>In situ</em> Raman spectroscopy further reveals that the high activity of EGOR is due to the generation of CoOOH species during the electrochemical reconstruction. Additionally, Fe incorporation has the effect of inhibiting the overoxidation of Co<sup>3+</sup>. This study successfully couples EGOR electrocatalysis with the production of valuable chemicals and hydrogen, providing new insights into high-performance EGOR catalytic systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116708"},"PeriodicalIF":6.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014715","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}
The swift development of polymer monomer leads to renewed interests in 1,3-propanediol (1,3-PDO) production by selective hydrogenating the methyl 3-hydroxypropionate (3-HPM). Heterogeneous CuNi catalysts can perform the reaction, but they deactivate easily and produce dehydration byproducts. We recently focus on the CuNi alloy center for efficient activation of the C=O bond in esters, which can be dedicated via the Localized Electronic Modulation on CuNi center in terms of subnanometric ceria. A fundamental mechanism is proved to create low-coordinated CeO2 (Ce-O coordination number of 4.1) and to stabilize the electron-deficient CuNi step sites by restrictive electron delivery. It results in the strengthened adsorption and activation of 3-HPM via the C=O bond, which obeys the Non-Dissociative Adsorption pathway. The Ce5-CuNi/SiO2 catalyst exhibits broad applicability to hydrogenate a variety of esters. It reaches 97 % 1,3-PDO yield at an ultra-fast rate of 3.73 mol3-HPM/molM/h with nice stability and facile regeneration.
{"title":"Localized electronic regulation on CuNi nanoalloys via subnanometric CeO2 for C=O activation in esters","authors":"Hao Liu, Wenhao Yang, Huibin Liu, Wenjun Zhu, Jingjie Luo, Changhai Liang","doi":"10.1016/j.jcat.2026.116707","DOIUrl":"10.1016/j.jcat.2026.116707","url":null,"abstract":"<div><div>The swift development of polymer monomer leads to renewed interests in 1,3-propanediol (1,3-PDO) production by selective hydrogenating the methyl 3-hydroxypropionate (3-HPM). Heterogeneous CuNi catalysts can perform the reaction, but they deactivate easily and produce dehydration byproducts. We recently focus on the CuNi alloy center for efficient activation of the C=O bond in esters, which can be dedicated via the Localized Electronic Modulation on CuNi center in terms of subnanometric ceria. A fundamental mechanism is proved to create low-coordinated CeO<sub>2</sub> (Ce-O coordination number of 4.1) and to stabilize the electron-deficient CuNi step sites by restrictive electron delivery. It results in the strengthened adsorption and activation of 3-HPM via the C=O bond, which obeys the Non-Dissociative Adsorption pathway. The Ce<sub>5</sub>-CuNi/SiO<sub>2</sub> catalyst exhibits broad applicability to hydrogenate a variety of esters. It reaches 97 % 1,3-PDO yield at an ultra-fast rate of 3.73 mol<sub>3-HPM</sub>/mol<sub>M</sub>/h with nice stability and facile regeneration.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116707"},"PeriodicalIF":6.5,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146000605","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 : 2026-01-16DOI: 10.1016/j.jcat.2026.116703
Haiyu Yao , Heng Zhang , Xuerong Shi, Shengming Zhang, Min Zhu, Haichao Xiong, Shusheng Xu
In the context of industrial-current density water electrolysis, material stability and catalytic activity remain critical challenges. Herein, a CoFeP/NF electrocatalyst enabled by pre-activation, hierarchical nanosheet architecture, bimetallic synergy, and carbon protection demonstrates good bifunctional OER/HER performance. The optimal CoFeP/NF requires overpotentials of 235 and 440 mV to achieve current densities of 10 and 2000 mA cm−2 for alkaline OER, respectively. In line with density-functional theory predictions, the CoFeP/NF also exhibits high alkaline HER activity, demanding an overpotential of 79 mV to reach 10 mA cm−2. The assembled CoFeP/NF||CoFeP/NF electrolyzer maintains stable operation for 1100 h at ∼200 mA cm−2. The comprehensive mechanism, encompassing the pre-activation mechanism, reaction kinetics, and origin of stability, has been meticulously investigated via the combination of theoretical calculations and in/ex-situ experimental characterizations. The findings offer a universal strategy for the rational design of efficient electrocatalysts for industrial-current–density water splitting.
在工业电流密度电解的背景下，材料的稳定性和催化活性仍然是关键的挑战。通过预活化、分层纳米片结构、双金属协同作用和碳保护，CoFeP/NF电催化剂表现出良好的双功能OER/HER性能。对于碱性OER，最佳CoFeP/NF需要235和440 mV的过电位才能分别达到10和2000 mA cm−2的电流密度。与密度泛函理论预测一致，CoFeP/NF也表现出高碱性HER活性，需要79 mV的过电位才能达到10 mA cm−2。组装的CoFeP/NF||CoFeP/NF电解槽在~ 200 mA cm−2下保持1100 h的稳定运行。综合机理，包括预活化机制，反应动力学和稳定性的起源，已经通过理论计算和原位/非原位实验表征的结合进行了细致的研究。这些发现为合理设计工业电流密度水分解的高效电催化剂提供了一种通用策略。
{"title":"Stable and efficient bifunctional cobalt-based phosphides for industrial-current water splitting: From multi-strategy engineering to mechanistic insights","authors":"Haiyu Yao , Heng Zhang , Xuerong Shi, Shengming Zhang, Min Zhu, Haichao Xiong, Shusheng Xu","doi":"10.1016/j.jcat.2026.116703","DOIUrl":"10.1016/j.jcat.2026.116703","url":null,"abstract":"<div><div>In the context of industrial-current density water electrolysis, material stability and catalytic activity remain critical challenges. Herein, a CoFeP/NF electrocatalyst enabled by pre-activation, hierarchical nanosheet architecture, bimetallic synergy, and carbon protection demonstrates good bifunctional OER/HER performance. The optimal CoFeP/NF requires overpotentials of 235 and 440 mV to achieve current densities of 10 and 2000 mA cm<sup>−2</sup> for alkaline OER, respectively. In line with density-functional theory predictions, the CoFeP/NF also exhibits high alkaline HER activity, demanding an overpotential of 79 mV to reach 10 mA cm<sup>−2</sup>. The assembled CoFeP/NF||CoFeP/NF electrolyzer maintains stable operation for 1100 h at ∼200 mA cm<sup>−2</sup>. The comprehensive mechanism, encompassing the pre-activation mechanism, reaction kinetics, and origin of stability, has been meticulously investigated via the combination of theoretical calculations and in/ex-situ experimental characterizations. The findings offer a universal strategy for the rational design of efficient electrocatalysts for industrial-current–density water splitting.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116703"},"PeriodicalIF":6.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993300","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 : 2026-01-16DOI: 10.1016/j.jcat.2026.116698
Zhenke Fan , Haiping Li , Kai Gao , Quanhua Deng , Yuguo Xia , Shu Liu , Yunbo Zang , Wanguo Hou
Oxygen vacancy (Ov)-containing semiconductors hold great promise for photocatalytic nitrogen fixation, as Ovs serve as efficient N2 activation centers. However, the low photocatalytic stability of Ovs has often been overlooked, and few strategies have been explored to enhance their stability. Moreover, methods to effectively create Ovs are still under investigation. Herein, crystalline structure transformation from BiOBr microplates to hierarchical Bi2MoO6 microplates consisting of sharp-end nanobelts was found to facilitate creation of Ovs in Bi2MoO6 during mannitol reduction. The Ov-containing Bi2MoO6 (Ov-BMO) exhibits improved photocatalytic nitrogen fixation activity but low stability in pure water. To enhance the stability and activity, the Ov-BMO/α-Co(OH)2 heterojunction was constructed to spatially separate Ovs and photogenerated holes and exhibits a solar-to-chemical conversion efficiency of 0.1% and an apparent quantum yield of 4.6% at 420 nm, which are among the top of the reported values. This work offers effective strategies for creating and stabilizing Ovs in Bi2MoO6 to boost photocatalytic nitrogen fixation.
{"title":"Structural transformation promoted oxygen vacancy creation and spatial separation of vacancies and holes in bismuth molybdate boost photocatalytic nitrogen fixation and stability","authors":"Zhenke Fan , Haiping Li , Kai Gao , Quanhua Deng , Yuguo Xia , Shu Liu , Yunbo Zang , Wanguo Hou","doi":"10.1016/j.jcat.2026.116698","DOIUrl":"10.1016/j.jcat.2026.116698","url":null,"abstract":"<div><div>Oxygen vacancy (Ov)-containing semiconductors hold great promise for photocatalytic nitrogen fixation, as Ovs serve as efficient N<sub>2</sub> activation centers. However, the low photocatalytic stability of Ovs has often been overlooked, and few strategies have been explored to enhance their stability. Moreover, methods to effectively create Ovs are still under investigation. Herein, crystalline structure transformation from BiOBr microplates to hierarchical Bi<sub>2</sub>MoO<sub>6</sub> microplates consisting of sharp-end nanobelts was found to facilitate creation of Ovs in Bi<sub>2</sub>MoO<sub>6</sub> during mannitol reduction. The Ov-containing Bi<sub>2</sub>MoO<sub>6</sub> (Ov-BMO) exhibits improved photocatalytic nitrogen fixation activity but low stability in pure water. To enhance the stability and activity, the Ov-BMO/α-Co(OH)<sub>2</sub> heterojunction was constructed to spatially separate Ovs and photogenerated holes and exhibits a solar-to-chemical conversion efficiency of 0.1% and an apparent quantum yield of 4.6% at 420 nm, which are among the top of the reported values. This work offers effective strategies for creating and stabilizing Ovs in Bi<sub>2</sub>MoO<sub>6</sub> to boost photocatalytic nitrogen fixation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116698"},"PeriodicalIF":6.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995785","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 : 2026-01-16DOI: 10.1016/j.jcat.2026.116702
Qianqian Shi , Keke He , Zhile Dang , Jing Zhang , Donghui Wei , Yu Lan
Discovering new radical generation mechanism and understanding origin of chemoselectivity of transformation reactions between the highly active radicals have been and continue to be the hot topics in radical chemistry. Different from the generally proposed single-electron transfer (SET) mechanism, the electron transfer along bond transformation (ETBT) mechanism has been suggested to be also possible and general for the radical reactions. To confirm this issue, the possible ETBT mechanisms and the theoretical method for chemoselectivity prediction of N-heterocyclic carbene (NHC)-catalyzed radical relay reactions have been systematically investigated by performing density functional theory (DFT) calculations. Herein, origin of chemoselectivity for these kinds of reactions has been explored by the distortion energy analysis, and a good linear relationship between the distortion energy (ΔEdist‡) and spin population change (Δe) of the radical species has been discovered for the first time. Furthermore, the Fukui function vector index has been successfully employed to predict chemical selectivity in radical relay reactions.
{"title":"Prediction on origin of chemoselectivity for N-Heterocyclic carbene (NHC)-catalyzed radical relay reactions","authors":"Qianqian Shi , Keke He , Zhile Dang , Jing Zhang , Donghui Wei , Yu Lan","doi":"10.1016/j.jcat.2026.116702","DOIUrl":"10.1016/j.jcat.2026.116702","url":null,"abstract":"<div><div>Discovering new radical generation mechanism and understanding origin of chemoselectivity of transformation reactions between the highly active radicals have been and continue to be the hot topics in radical chemistry. Different from the generally proposed single-electron transfer (SET) mechanism, the electron transfer along bond transformation (ETBT) mechanism has been suggested to be also possible and general for the radical reactions. To confirm this issue, the possible ETBT mechanisms and the theoretical method for chemoselectivity prediction of N-heterocyclic carbene (NHC)-catalyzed radical relay reactions have been systematically investigated by performing density functional theory (DFT) calculations. Herein, origin of chemoselectivity for these kinds of reactions has been explored by the distortion energy analysis, and a good linear relationship between the distortion energy (Δ<em>E</em><sub>dist</sub><sup>‡</sup>) and spin population change (Δ<em>e</em>) of the radical species has been discovered for the first time. Furthermore, the Fukui function vector index has been successfully employed to predict chemical selectivity in radical relay reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116702"},"PeriodicalIF":6.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995784","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 : 2026-01-16DOI: 10.1016/j.jcat.2026.116693
Yi Hu , Xiangzhu Yu , Meng Miao, Chenlai Guo, Xueying Tang, Enshuang Bai, Yingyu Jiang, Lianyue Wang
The development of a mild and efficient non-noble metal heterogeneous catalytic system to achieve the conversion of nitroaromatic compounds into high-value products is of great significance, but it remains a substantial challenge. In this study, we present a mild and efficient protocol for the selective N-formylation of nitroarenes over a nitrogen-doped mesoporous carbon-supported iron-based catalyst Fe-opd-900, which was prepared by the method of high-temperature pyrolysis with the sacrifice of the template agent. Various substrates were successfully converted into the desired target products in moderate to excellent yields utilizing versatile formic acid as both a renewable hydrogen carrier and C1 source under mild conditions. The robust catalyst Fe-opd-900 could be used continuously for 15 times without significant loss in catalytic activity. The existence of atomically dispersed iron centers was confirmed by the characterizations of XPS, aberration-corrected HAADF-STEM, XANES, and EXAFS. Characterization and active sites studies indicate that the nitrogen species and highly dispersed Fe-Nx are crucial for the efficient activation of formic acid and the enhancement of catalytic performance. Based on kinetic experiments and control experiments, a reasonable reaction mechanism was proposed.
{"title":"Atomic-scale iron catalyst for the reductive N-formylation of nitroarenes under mild conditions","authors":"Yi Hu , Xiangzhu Yu , Meng Miao, Chenlai Guo, Xueying Tang, Enshuang Bai, Yingyu Jiang, Lianyue Wang","doi":"10.1016/j.jcat.2026.116693","DOIUrl":"10.1016/j.jcat.2026.116693","url":null,"abstract":"<div><div>The development of a mild and efficient non-noble metal heterogeneous catalytic system to achieve the conversion of nitroaromatic compounds into high-value products is of great significance, but it remains a substantial challenge. In this study, we present a mild and efficient protocol for the selective <em>N</em>-formylation of nitroarenes over a nitrogen-doped mesoporous carbon-supported iron-based catalyst Fe-opd-900, which was prepared by the method of high-temperature pyrolysis with the sacrifice of the template agent. Various substrates were successfully converted into the desired target products in moderate to excellent yields utilizing versatile formic acid as both a renewable hydrogen carrier and C1 source under mild conditions. The robust catalyst Fe-opd-900 could be used continuously for 15 times without significant loss in catalytic activity. The existence of atomically dispersed iron centers was confirmed by the characterizations of XPS, aberration-corrected HAADF-STEM, XANES, and EXAFS. Characterization and active sites studies indicate that the nitrogen species and highly dispersed Fe-N<sub>x</sub> are crucial for the efficient activation of formic acid and the enhancement of catalytic performance. Based on kinetic experiments and control experiments, a reasonable reaction mechanism was proposed.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116693"},"PeriodicalIF":6.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993180","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 : 2026-01-14DOI: 10.1016/j.jcat.2026.116696
Han Wang , Yaopeng Xiao , Hanbo Yu , Hong Qin , Ziwei Wang , Guangming Zeng , Piao Xu
Exploring heterojunction photocatalysts with multi-functionalities is of great importance for clean energy production and environmental remediation. Herein, a new type of step (S)-scheme heterojunction photocatalyst based on metal–organic frameworks (MOFs, NH2-UIO-66) and covalent organic frameworks (COFs, TpMa) was developed by in-suit synthesis. Experimental data along with the density functional theory calculation confirmed the formation of internal electric field (IEF) directing from TpMa to NH2-UIO-66 upon hybridization. The S-scheme charge transfer path enables the enhancement of surface charge transfer efficiency as well as the prolongation of injected electron lifetime, thereby constraining the recombination rate of charge carriers. As a result, the optimized hybrid shows a robust H2O2 evolution of 23.04 mM h−1 g−1 with an apparent quantum efficiency of 4.15 % at 420 nm, and 83.4 % degradation of tetracycline in a 60 min reaction time, which far exceeded those of pristine NH2-UIO-66. This study opens up a new avenue for the construction of MOF-COF heterojunctions with promising applications.
{"title":"In-suit growth of MOFs on COFs: Construction of an effective bifunctional hybrid photocatalyst with accelerated electron transfer","authors":"Han Wang , Yaopeng Xiao , Hanbo Yu , Hong Qin , Ziwei Wang , Guangming Zeng , Piao Xu","doi":"10.1016/j.jcat.2026.116696","DOIUrl":"10.1016/j.jcat.2026.116696","url":null,"abstract":"<div><div>Exploring heterojunction photocatalysts with multi-functionalities is of great importance for clean energy production and environmental remediation. Herein, a new type of step (S)-scheme heterojunction photocatalyst based on metal–organic frameworks (MOFs, NH<sub>2</sub>-UIO-66) and covalent organic frameworks (COFs, TpMa) was developed by in-suit synthesis. Experimental data along with the density functional theory calculation confirmed the formation of internal electric field (IEF) directing from TpMa to NH<sub>2</sub>-UIO-66 upon hybridization. The S-scheme charge transfer path enables the enhancement of surface charge transfer efficiency as well as the prolongation of injected electron lifetime, thereby constraining the recombination rate of charge carriers. As a result, the optimized hybrid shows a robust H<sub>2</sub>O<sub>2</sub> evolution of 23.04 mM h<sup>−1</sup> g<sup>−1</sup> with an apparent quantum efficiency of 4.15 % at 420 nm, and 83.4 % degradation of tetracycline in a 60 min reaction time, which far exceeded those of pristine NH<sub>2</sub>-UIO-66. This study opens up a new avenue for the construction of MOF-COF heterojunctions with promising applications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116696"},"PeriodicalIF":6.5,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995797","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 : 2026-01-13DOI: 10.1016/j.jcat.2026.116700
Tian-Cai Yue, Xin-Fang Wang, Jian-Bo Huang, Lu-Lu Wang, Duo-Zhi Wang
Four new Co(II)-based metal–organic frameworks (MOFs) were successfully synthesized by a mixed ligand strategy. The controllable transformation of the bridging groups in the secondary structural units was achieved by modulating the anions in MOFs 1–4. The catalytic performance study indicated that MOF 1 exhibited excellent photocatalytic activity for the oxidation of sulfides to sulfoxides under the air atmosphere and •O2− and 1O2 were the main active species in the photocatalytic reaction process. Furthermore, MOF 1 also could efficiently catalyze the carboxylative cyclization of propargylic amines with CO2 and the possible catalytic mechanism was explored in detail. Importantly, MOF 1 can exhibit remarkable catalytic activity after five cycles in both reactions. Therefore, MOF 1 can be used as an efficient and stable heterogeneous catalyst for the oxidation of sulfides and the carboxylative cyclization of propargylic amines with CO2.
{"title":"Assembly of functional Co(II)−organic frameworks through a mixed ligand strategy: structure, photocatalytic oxidation of sulfides and CO2 conversion","authors":"Tian-Cai Yue, Xin-Fang Wang, Jian-Bo Huang, Lu-Lu Wang, Duo-Zhi Wang","doi":"10.1016/j.jcat.2026.116700","DOIUrl":"10.1016/j.jcat.2026.116700","url":null,"abstract":"<div><div>Four new Co(II)-based metal–organic frameworks (MOFs) were successfully synthesized by a mixed ligand strategy. The controllable transformation of the bridging groups in the secondary structural units was achieved by modulating the anions in MOFs <strong>1</strong>–<strong>4</strong>. The catalytic performance study indicated that MOF <strong>1</strong> exhibited excellent photocatalytic activity for the oxidation of sulfides to sulfoxides under the air atmosphere and •O<sub>2</sub><sup>−</sup> and <sup>1</sup>O<sub>2</sub> were the main active species in the photocatalytic reaction process. Furthermore, MOF <strong>1</strong> also could efficiently catalyze the carboxylative cyclization of propargylic amines with CO<sub>2</sub> and the possible catalytic mechanism was explored in detail. Importantly, MOF <strong>1</strong> can exhibit remarkable catalytic activity after five cycles in both reactions. Therefore, MOF <strong>1</strong> can be used as an efficient and stable heterogeneous catalyst for the oxidation of sulfides and the carboxylative cyclization of propargylic amines with CO<sub>2</sub>.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116700"},"PeriodicalIF":6.5,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145961877","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 : 2026-01-13DOI: 10.1016/j.jcat.2026.116694
Wen-Lin Zou, Zhi Guan, Yan-Hong He
A photoredox-catalyzed three-component reaction has been developed, in which two distinct nitrogen-centered radicals are generated through sequential reductive and oxidative processes mediated by the photocatalyst. This transformation involves C–C bond cleavage and generation of an α‑aminoalkyl radical as parallel key steps, enabling alkene difunctionalization to achieve N-α-alkylation at the α-C(sp3)-H site of N-aryl glycine derivatives. This method offers a novel approach for the synthesis of unnatural amino acids bearing diverse functional groups. The reaction proceeds under mild conditions and exhibits broad substrate scope, facilitating the preparation of a series of N-aryl glycine derivatives containing cyanoalkyl groups.
建立了光氧化催化的三组分反应，在该反应中，光催化剂介导的连续还原和氧化过程产生了两种不同的氮中心自由基。这种转化包括C-C键的裂解和α-氨基烷基自由基的生成作为平行的关键步骤，使烯烃二官能化在N-芳基甘氨酸衍生物的α- c (sp3)-H位点实现N-α-烷基化。该方法为合成具有不同官能团的非天然氨基酸提供了新的途径。该反应在温和的条件下进行，具有广泛的底物范围，有利于制备一系列含有氰烷基的n -芳基甘氨酸衍生物。
{"title":"Photoredox-catalyzed three-component cyanoalkylation of glycine derivatives: Enabled by dual nitrogen-centered radicals","authors":"Wen-Lin Zou, Zhi Guan, Yan-Hong He","doi":"10.1016/j.jcat.2026.116694","DOIUrl":"10.1016/j.jcat.2026.116694","url":null,"abstract":"<div><div>A photoredox-catalyzed three-component reaction has been developed, in which two distinct nitrogen-centered radicals are generated through sequential reductive and oxidative processes mediated by the photocatalyst. This transformation involves C–C bond cleavage and generation of an α‑aminoalkyl radical as parallel key steps, enabling alkene difunctionalization to achieve <em>N</em>-α-alkylation at the α-C(sp<sup>3</sup>)-H site of <em>N</em>-aryl glycine derivatives. This method offers a novel approach for the synthesis of unnatural amino acids bearing diverse functional groups. The reaction proceeds under mild conditions and exhibits broad substrate scope, facilitating the preparation of a series of <em>N</em>-aryl glycine derivatives containing cyanoalkyl groups.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116694"},"PeriodicalIF":6.5,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962567","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 : 2026-01-12DOI: 10.1016/j.jcat.2026.116695
Yaqian Zhang , Xingxu Wang , Bingying Han , Lixia Ling , Baojun Wang , Maohong Fan , Riguang Zhang
The oxidative coupling of methane (OCM) reaction is hindered by fundamental scientific challenges including the difficulty in CH4 activation and the inability to inhibit deep oxidation. In this study, the LaAlO3 catalyst, which exhibits excellent low-temperature activity and thermal stability, was selected. The structure–activity relationship among the catalyst surface structure, surface oxygen species, and reaction performance was systematically explored using DFT calculations and microkinetic modeling. The results indicate that different surface terminations (LaO- and AlO2-terminations) of LaAlO3 catalyst exhibit distinct oxygen species. The evolution pathway of oxygen species on the LaO-termination surface proceeds as O2–→O2–→O22–→O2–, while on the AlO2-termination surface it follows O2–→O22–→O2–. Among these oxygen species, O2– plays a dominant role in CH4 dissociation. The LaO-termination demonstrates three major advantages: higher CH4 dissociation activity, superior C2H4 production activity, and enhanced selectivity, establishing it as the dominant active termination. Doping the LaO-termination catalysts with alkaline earth metals (Mg, Ca, Sr) do not alter the types of oxygen species but significantly modulate reaction characteristics. Bader charge of surface O2– serves as an effective descriptor for predicting CH4 dissociation capability of M/LaO-p-O2– catalysts. Under realistic conditions, due to fewer surface free sites, Ca/LaO-p-O2– exhibits a lower C2H4 formation rate than Sr/LaO-p-O2–.
{"title":"Unraveling the evolution of oxygen species and its role in adjusting catalytic performance over LaAlO3-based catalysts in oxidative coupling of methane","authors":"Yaqian Zhang , Xingxu Wang , Bingying Han , Lixia Ling , Baojun Wang , Maohong Fan , Riguang Zhang","doi":"10.1016/j.jcat.2026.116695","DOIUrl":"10.1016/j.jcat.2026.116695","url":null,"abstract":"<div><div>The oxidative coupling of methane (OCM) reaction is hindered by fundamental scientific challenges including the difficulty in CH<sub>4</sub> activation and the inability to inhibit deep oxidation. In this study, the LaAlO<sub>3</sub> catalyst, which exhibits excellent low-temperature activity and thermal stability, was selected. The structure–activity relationship among the catalyst surface structure, surface oxygen species, and reaction performance was systematically explored using DFT calculations and microkinetic modeling. The results indicate that different surface terminations (LaO- and AlO<sub>2</sub>-terminations) of LaAlO<sub>3</sub> catalyst exhibit distinct oxygen species. The evolution pathway of oxygen species on the LaO-termination surface proceeds as O<sup>2–</sup>→O<sub>2</sub><sup>–</sup>→O<sub>2</sub><sup>2–</sup>→O<sup>2–</sup>, while on the AlO<sub>2</sub>-termination surface it follows O<sup>2–</sup>→O<sub>2</sub><sup>2–</sup>→O<sup>2–</sup>. Among these oxygen species, O<sup>2–</sup> plays a dominant role in CH<sub>4</sub> dissociation. The LaO-termination demonstrates three major advantages: higher CH<sub>4</sub> dissociation activity, superior C<sub>2</sub>H<sub>4</sub> production activity, and enhanced selectivity, establishing it as the dominant active termination. Doping the LaO-termination catalysts with alkaline earth metals (Mg, Ca, Sr) do not alter the types of oxygen species but significantly modulate reaction characteristics. Bader charge of surface O<sup>2–</sup> serves as an effective descriptor for predicting CH<sub>4</sub> dissociation capability of M/LaO-p-O<sup>2–</sup> catalysts. Under realistic conditions, due to fewer surface free sites, Ca/LaO-p-O<sup>2–</sup> exhibits a lower C<sub>2</sub>H<sub>4</sub> formation rate than Sr/LaO-p-O<sup>2–</sup>.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116695"},"PeriodicalIF":6.5,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956885","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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