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}
Pub Date : 2026-01-12DOI: 10.1016/j.jcat.2026.116697
Hong Wang , Yan Wang , Yong Jia , Lina Guo , Gang Cheng , Zhongming Wang , Kai Yang , Wenxin Dai
Research on the photocatalytic production of H2 from HCOOH decomposition provides scientific guidance for hydrogen energy development. In this study, a Pd-doped oxygen-deficient TiO2 catalyst featuring mixed-valence PdOx atomic cluster nests, oxygen vacancies (Vo), and hydroxyl groups was synthesized. Activity tests revealed that 0.4 Pd-def-TiO2 sample performed best under visible light, producing H2 at a rate of 3180.66 μmol·g−1·h−1, a 124-fold enhancement over def-TiO2. Combined characterization and theoretical calculation results showed that Pd-def-TiO2 formed a “step-like” energy band structure, and the separation and transfer of photogenerated carriers have been optimized in conjunction with Vo and surface hydroxyl groups. Further, HCOOH adsorption was followed by the formation of a bidentate HCOOBX species, in which one oxygen atom of the adsorbate was hydrogen bonded with a surface hydroxyl group, while the other end was adsorbed onto a Pd0 site. This process involved simultaneous electron loss and gain, resulting in a distinctive “valley-shaped” gas-sensing response, thus promoting directional activation of HCOOH, facilitating complete redox reactions. Moreover, photoreduction and Vo (near Pd sites) promoted electron delocalization in mixed-valent Pd2+/Pd0 species, enabling self-cycling of these active sites, leading to enhanced efficiency and stability during photocatalytic hydrogen evolution from HCOOH. This study contributes to the design of highly efficient and stable catalysts, and advances the understanding of the underlying reaction mechanisms.
{"title":"Photocatalytic H2 production from HCOOH over Pd/TiO2: Pd2+/Pd0 self-cycle and adsorption-induced electron transfer mechanism","authors":"Hong Wang , Yan Wang , Yong Jia , Lina Guo , Gang Cheng , Zhongming Wang , Kai Yang , Wenxin Dai","doi":"10.1016/j.jcat.2026.116697","DOIUrl":"10.1016/j.jcat.2026.116697","url":null,"abstract":"<div><div>Research on the photocatalytic production of H<sub>2</sub> from HCOOH decomposition provides scientific guidance for hydrogen energy development. In this study, a Pd-doped oxygen-deficient TiO<sub>2</sub> catalyst featuring mixed-valence PdO<sub>x</sub> atomic cluster nests, oxygen vacancies (Vo), and hydroxyl groups was synthesized. Activity tests revealed that 0.4 Pd-def-TiO<sub>2</sub> sample performed best under visible light, producing H<sub>2</sub> at a rate of 3180.66 μmol·g<sup>−1</sup>·h<sup>−1</sup>, a 124-fold enhancement over def-TiO<sub>2</sub>. Combined characterization and theoretical calculation results showed that Pd-def-TiO<sub>2</sub> formed a “step-like” energy band structure, and the separation and transfer of photogenerated carriers have been optimized in conjunction with Vo and surface hydroxyl groups. Further, HCOOH adsorption was followed by the formation of a bidentate HCOO<sub>BX</sub> species, in which one oxygen atom of the adsorbate was hydrogen bonded with a surface hydroxyl group, while the other end was adsorbed onto a Pd<sup>0</sup> site. This process involved simultaneous electron loss and gain, resulting in a distinctive “valley-shaped” gas-sensing response, thus promoting directional activation of HCOOH, facilitating complete redox reactions. Moreover, photoreduction and Vo (near Pd sites) promoted electron delocalization in mixed-valent Pd<sup>2+</sup>/Pd<sup>0</sup> species, enabling self-cycling of these active sites, leading to enhanced efficiency and stability during photocatalytic hydrogen evolution from HCOOH. This study contributes to the design of highly efficient and stable catalysts, and advances the understanding of the underlying reaction mechanisms.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116697"},"PeriodicalIF":6.5,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956884","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.2026.116701
Mohammad Bashiri, Mona Hosseini-Sarvari
In the present study, a novel benzimidazole ligand was synthesized and used as a precursor for the preparation of iron(II) complex. Following the synthesis, a comprehensive array of experimental investigations was undertaken to explore the structural, photo-electronic, and electrochemical characteristics of the iron(II) complex. The complex was subsequently utilized as an efficient photocatalyst for the selective synthesis of 5-hydroxymethylfurfural (HMF) from fructose. In this catalytic process, a luminescent solar concentrator (LSC) system was employed, further augmented by plant-derived quantum dots. This innovative optical system significantly enhanced the overall efficiency of the photocatalytic reaction. We selected a colorless transparent panel for the LSC device because the emission from the quantum dots falls within the blue region, which overlaps with the absorption spectrum of our complex and can promote the progress of the reaction. The yield of 5-hydroxymethylfurfural from fructose in this continuous flow system under solar irradiation was 91%, whereas in the batch system, a yield of only 70% was achieved under blue light irradiation. Furthermore, this work contributes novel insights into the potential of iron(II) complex-based photocatalysts for driving intricate chemical transformations under environmentally benign and sustainable conditions.
{"title":"Bio-derived quantum dot based luminescent solar concentrator for photocatalytic conversion of fructose to 5-hydroxymethylfurfural via iron(II) complex catalysis","authors":"Mohammad Bashiri, Mona Hosseini-Sarvari","doi":"10.1016/j.jcat.2026.116701","DOIUrl":"10.1016/j.jcat.2026.116701","url":null,"abstract":"<div><div>In the present study, a novel benzimidazole ligand was synthesized and used as a precursor for the preparation of iron(II) complex. Following the synthesis, a comprehensive array of experimental investigations was undertaken to explore the structural, photo-electronic, and electrochemical characteristics of the iron(II) complex. The complex was subsequently utilized as an efficient photocatalyst for the selective synthesis of 5-hydroxymethylfurfural (HMF) from fructose. In this catalytic process, a luminescent solar concentrator (LSC) system was employed, further augmented by plant-derived quantum dots. This innovative optical system significantly enhanced the overall efficiency of the photocatalytic reaction. We selected a colorless transparent panel for the LSC device because the emission from the quantum dots falls within the blue region, which overlaps with the absorption spectrum of our complex and can promote the progress of the reaction. The yield of 5-hydroxymethylfurfural from fructose in this continuous flow system under solar irradiation was 91%, whereas in the batch system, a yield of only 70% was achieved under blue light irradiation. Furthermore, this work contributes novel insights into the potential of iron(II) complex-based photocatalysts for driving intricate chemical transformations under environmentally benign and sustainable conditions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116701"},"PeriodicalIF":6.5,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956886","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.2026.116699
Chenglong Liang , Shuwen Huan , Xiong Chen , Jimmy C. Yu , Meifang Zheng , Sibo Wang
Catalytic oxidation of alcohols to the corresponding carbonyl compounds represents a fundamental transformation in the chemical industry. Herein, we report a novel type-II heterojunction comprising CdS quantum dots (QDs) anchored on boron-doped carbon nitride (BCN) nanosheets is explored for the photocatalytic selective oxidation of benzylic alcohols under an ambient CO2 atmosphere. The CdS QDs/BCN system manifests substantially enhanced performance, achieving 81% yield of benzaldehyde with 99% selectivity, much higher than either bare BCN or CdS QDs. In this catalytic system, CO2 is adsorbed and activated at the surface basic sites of CdS QDs/BCN, forming the key carbonate intermediates with benzylic alcohols, which are then selectively oxidized by photoinduced holes, accompanied by the release of CO2. The protocol demonstrates acceptorless dehydrogenation using CO2 as an electron shuttle, providing a green and efficient strategy for oxidant-free alcohol oxidation.
{"title":"CO2-promoted photocatalytic oxidation of benzylic alcohols over CdS/boron-doped carbon nitride","authors":"Chenglong Liang , Shuwen Huan , Xiong Chen , Jimmy C. Yu , Meifang Zheng , Sibo Wang","doi":"10.1016/j.jcat.2026.116699","DOIUrl":"10.1016/j.jcat.2026.116699","url":null,"abstract":"<div><div>Catalytic oxidation of alcohols to the corresponding carbonyl compounds represents a fundamental transformation in the chemical industry. Herein, we report a novel type-II heterojunction comprising CdS quantum dots (QDs) anchored on boron-doped carbon nitride (BCN) nanosheets is explored for the photocatalytic selective oxidation of benzylic alcohols under an ambient CO<sub>2</sub> atmosphere. The CdS QDs/BCN system manifests substantially enhanced performance, achieving 81% yield of benzaldehyde with 99% selectivity, much higher than either bare BCN or CdS QDs. In this catalytic system, CO<sub>2</sub> is adsorbed and activated at the surface basic sites of CdS QDs/BCN, forming the key carbonate intermediates with benzylic alcohols, which are then selectively oxidized by photoinduced holes, accompanied by the release of CO<sub>2</sub>. The protocol demonstrates acceptorless dehydrogenation using CO<sub>2</sub> as an electron shuttle, providing a green and efficient strategy for oxidant-free alcohol oxidation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116699"},"PeriodicalIF":6.5,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956883","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 : 2026-01-08DOI: 10.1016/j.jcat.2026.116688
Liping Tan, Li Fang, Yao Zhang, Jinglin Tong, Yuxin Zhuang, Chunya Li, Lianqing Chen, Shiwei Jin
Environmentally friendly liquid-phase selective oxidation of alcohols with oxygen as oxidant agent is a green strategy for synthesising nitriles and amides. Therein, the design and preparation of heterogeneous catalysts with high activity and selectivity is a hot research topic in this field. Here, we report that nitrogen-doped manganese oxide catalysts have been synthesized by a hydrothermal method, which can oxidize benzyl alcohol to synthesize benzonitrile and benzamide in a cyanide-free environment with high efficiency. As the reaction time and temperature were 6 h and 150 °C, the conversion of benzyl alcohol (feed dosage: 1 mmol) and the selectivity of benzamide were >99 % and 94 %, respectively. The catalyst could be reused at least 5 times without significantly reducing activity. Additionally, the catalyst exhibits broad applicability, capable of catalyzing the cyanidation of various aromatic and aliphatic alcohols. The enhancement in N-MnO2 catalyst performance is attributed to the introduction of nitrogen, which increases the content of low-valent manganese and oxygen vacancies within the catalyst. It contributes to improved selectivity for benzamide.
{"title":"Nitrogen-doped manganese oxide catalysts boost oxidative cyanation of benzyl alcohols","authors":"Liping Tan, Li Fang, Yao Zhang, Jinglin Tong, Yuxin Zhuang, Chunya Li, Lianqing Chen, Shiwei Jin","doi":"10.1016/j.jcat.2026.116688","DOIUrl":"10.1016/j.jcat.2026.116688","url":null,"abstract":"<div><div>Environmentally friendly liquid-phase selective oxidation of alcohols with oxygen as oxidant agent is a green strategy for synthesising nitriles and amides. Therein, the design and preparation of heterogeneous catalysts with high activity and selectivity is a hot research topic in this field. Here, we report that nitrogen-doped manganese oxide catalysts have been synthesized by a hydrothermal method, which can oxidize benzyl alcohol to synthesize benzonitrile and benzamide in a cyanide-free environment with high efficiency. As the reaction time and temperature were 6 h and 150 °C, the conversion of benzyl alcohol (feed dosage: 1 mmol) and the selectivity of benzamide were >99 % and 94 %, respectively. The catalyst could be reused at least 5 times without significantly reducing activity. Additionally, the catalyst exhibits broad applicability, capable of catalyzing the cyanidation of various aromatic and aliphatic alcohols. The enhancement in N-MnO<sub>2</sub> catalyst performance is attributed to the introduction of nitrogen, which increases the content of low-valent manganese and oxygen vacancies within the catalyst. It contributes to improved selectivity for benzamide.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116688"},"PeriodicalIF":6.5,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920099","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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