首页 > 最新文献

Journal of Catalysis最新文献

英文 中文
Layered double hydroxides enabled efficient electrocatalytic oxidative cleavage of C(OH)−C bonds 层状双氢氧化物实现了C(OH)−C键的高效电催化氧化裂解
IF 7.3 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-31 DOI: 10.1016/j.jcat.2026.116728
Yiyuan Zhang, Xianhong Wu, Jinjie Lin, Hanyang Chen, Run-Cang Sun
The electrochemical oxidative cleavage of C(OH)-C bonds facilitates the conversion of lignin-derived secondary alcohols and ketones into valuable carboxylates in a mild and environmentally friendly manner. In this study, we present efficient and cost-effective FeNi layered double-hydroxide (LDH) nanosheets created through a one-step galvanostatic electrodeposition on nickel foam (NF). The FeNi-LDH/NF shows a high activity for α-phenethyl alcohol (α-PEA) electrooxidation reaction leading to low potential 1.489 V vs. RHE to reach a current density of 100 mA cm−2, α-PEA was almost completely transformed, and the yield of benzoic acid (BA) was high (> 95%). Both theory and experiments show that α-PEA is first oxidized to acetophenone and then to benzoic acid. The dehydrogenation and oxygenation of the C–H bond is the rate-limiting step of the reaction. In addition, an energy-saving and multifunctional flow electrolytic cell has been developed successfully, througn coupling α-PEA electrooxidation reaction with hydrogen evolution reaction, with FeNi-LDH/NF as dual-functional electrocatalyst. The flow electrolytic cell can operate stably for 200 h.
C(OH)-C键的电化学氧化裂解有助于木质素衍生的仲醇和酮以温和和环保的方式转化为有价值的羧酸盐。在这项研究中,我们通过一步恒流电沉积在泡沫镍(NF)上制备了高效且具有成本效益的FeNi层状双氢氧化物(LDH)纳米片。FeNi-LDH/NF对α-苯乙醇(α-PEA)具有较高的电氧化反应活性,相对于RHE电位为1.489 V,电流密度为100 mA cm−2,α-PEA几乎完全转化,苯甲酸(BA)收率高(95%)。理论和实验都表明,α-PEA首先被氧化为苯乙酮,然后被氧化为苯甲酸。C-H键的脱氢和氧化是反应的限速步骤。此外,通过α-PEA电氧化反应与析氢反应耦合,以FeNi-LDH/NF为双功能电催化剂,成功研制出节能多功能流动电解槽。流动电解槽可稳定运行200 h。
{"title":"Layered double hydroxides enabled efficient electrocatalytic oxidative cleavage of C(OH)−C bonds","authors":"Yiyuan Zhang, Xianhong Wu, Jinjie Lin, Hanyang Chen, Run-Cang Sun","doi":"10.1016/j.jcat.2026.116728","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116728","url":null,"abstract":"The electrochemical oxidative cleavage of C(OH)-C bonds facilitates the conversion of lignin-derived secondary alcohols and ketones into valuable carboxylates in a mild and environmentally friendly manner. In this study, we present efficient and cost-effective FeNi layered double-hydroxide (LDH) nanosheets created through a one-step galvanostatic electrodeposition on nickel foam (NF). The FeNi-LDH/NF shows a high activity for α-phenethyl alcohol (α-PEA) electrooxidation reaction leading to low potential 1.489 V vs. RHE to reach a current density of 100 mA cm<sup>−2</sup>, α-PEA was almost completely transformed, and the yield of benzoic acid (BA) was high (&gt; 95%). Both theory and experiments show that α-PEA is first oxidized to acetophenone and then to benzoic acid. The dehydrogenation and oxygenation of the C–H bond is the rate-limiting step of the reaction. In addition, an energy-saving and multifunctional flow electrolytic cell has been developed successfully, througn coupling α-PEA electrooxidation reaction with hydrogen evolution reaction, with FeNi-LDH/NF as dual-functional electrocatalyst. The flow electrolytic cell can operate stably for 200 h.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"4 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095952","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}
引用次数: 0
Modulating Cu electrode microenvironments with MOF coatings: insights from molecular dynamics and electrochemical experiments of CO reduction 用MOF涂层调制Cu电极微环境:来自分子动力学和CO还原电化学实验的见解
IF 7.3 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-30 DOI: 10.1016/j.jcat.2026.116723
Manish Maurya, Hannah Fejzić, Xavier C. Krull, Huy Nguyen, Matthew Neurock, Joseph T. Hupp, Chibueze V. Amanchukwu, Rachel B. Getman
{"title":"Modulating Cu electrode microenvironments with MOF coatings: insights from molecular dynamics and electrochemical experiments of CO reduction","authors":"Manish Maurya, Hannah Fejzić, Xavier C. Krull, Huy Nguyen, Matthew Neurock, Joseph T. Hupp, Chibueze V. Amanchukwu, Rachel B. Getman","doi":"10.1016/j.jcat.2026.116723","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116723","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"8 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089693","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}
引用次数: 0
Y-induced oxygen vacancy engineering and local electronic reconstruction for enhanced ammonia decomposition over Ni1Ce1-xYxOα Ni1Ce1-xYxOα上y诱导氧空位工程和局部电子重构促进氨分解
IF 7.3 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-30 DOI: 10.1016/j.jcat.2026.116718
Zhixian Bao, Huibin Liu, Yizhou Zhang, Zhiheng Wang, Hao Li, Haoquan Hu
{"title":"Y-induced oxygen vacancy engineering and local electronic reconstruction for enhanced ammonia decomposition over Ni1Ce1-xYxOα","authors":"Zhixian Bao, Huibin Liu, Yizhou Zhang, Zhiheng Wang, Hao Li, Haoquan Hu","doi":"10.1016/j.jcat.2026.116718","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116718","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"86 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089810","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}
引用次数: 0
A tandem visible-light/heterogeneous-alumina catalytic platform for sustainable transition-metal-free cyclobutene synthesis 可见光/多相氧化铝串联催化平台可持续合成无过渡金属环丁烯
IF 7.3 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-28 DOI: 10.1016/j.jcat.2026.116726
Zhe Wang, Jie Huang, Min Zhou, Lin Ma, Min Zhang
{"title":"A tandem visible-light/heterogeneous-alumina catalytic platform for sustainable transition-metal-free cyclobutene synthesis","authors":"Zhe Wang, Jie Huang, Min Zhou, Lin Ma, Min Zhang","doi":"10.1016/j.jcat.2026.116726","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116726","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"78 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071915","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}
引用次数: 0
Understanding metal-support interaction for single-walled carbon nanotube synthesis: a comparative study of Co on MgO and Al2O3 了解单壁碳纳米管合成中金属-载体相互作用:Co对MgO和Al2O3的比较研究
IF 7.3 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-28 DOI: 10.1016/j.jcat.2026.116722
Jiwoo Kim, Dong Hwan Kim, Seungki Hong, Tae Hoon Seo, Jaegeun Lee
{"title":"Understanding metal-support interaction for single-walled carbon nanotube synthesis: a comparative study of Co on MgO and Al2O3","authors":"Jiwoo Kim, Dong Hwan Kim, Seungki Hong, Tae Hoon Seo, Jaegeun Lee","doi":"10.1016/j.jcat.2026.116722","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116722","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"8 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072539","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}
引用次数: 0
Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides 氮化硼纳米管负载过渡金属氧化物催化CO氧化过程中表面物质的作用
IF 7.3 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-28 DOI: 10.1016/j.jcat.2026.116715
Jinwon Choi, Mireu Kim, Yeonsu Kwak, Amol Pophali, Gary Halada, Huiting Luo, Gihan Kwon, Insoo Ro, Jaewoo Kim, Miriam Rafailovich, Taejin Kim
{"title":"Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides","authors":"Jinwon Choi, Mireu Kim, Yeonsu Kwak, Amol Pophali, Gary Halada, Huiting Luo, Gihan Kwon, Insoo Ro, Jaewoo Kim, Miriam Rafailovich, Taejin Kim","doi":"10.1016/j.jcat.2026.116715","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116715","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"75 1","pages":"116715"},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072540","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}
引用次数: 0
Metal nitrate in acetonitrile-driven aerobic oxidative cleavage of alkynes to carboxylic acids under mild conditions 金属硝酸盐在乙腈驱动的有氧氧化裂解条件下生成羧酸
IF 7.3 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1016/j.jcat.2026.116719
Chao Xie, Zejun Liu, Huichao Wang, Qidong Hou, Hengli Qian, Zhiwei Jiang, Meiting Ju
CC bond cleavage in alkynes provides a powerful strategy for the functional group transformation of alkyne compounds, but it is challenging to balance reactivity and selectivity due to its high bond dissociation energy and inherently complex reaction pathways. In this work, we report the use of commercially available nitrates in acetonitrile for the mild aerobic oxidative cleavage of the alkyne CC bonds, resulting in the formation of carboxylic acids with good to excellent yields. This approach demonstrates broad functional group tolerance, applicable to those unactivated alkynes and substrates containing oxidation-sensitive groups. Mechanistic studies using EPR, FT-IR, and NMR measurements reveal that the excellent catalytic property arises from the formation of coordination intermediates between the alkyne and zinc nitrate, stabilized by acetonitrile through ion–dipole interactions. This stabilization promotes alkyne activation, facilitates the oxygen atom transfer (OAT) from nitrate to the CC bond and reduces the nitrate to nitrogen oxides, which then act as free-radical initiators to trigger a chain reaction and accelerate the oxidative cleavage of the CC bond, with molecular oxygen serving as the terminal oxidant.
烷烃中CC键的裂解为烷烃化合物的官能团转化提供了一种强有力的策略,但由于其高键解离能和固有的复杂反应途径,很难平衡反应性和选择性。在这项工作中,我们报道了在乙腈中使用市售硝酸盐对炔CC键进行温和的有氧氧化裂解,从而形成收率良好到优异的羧酸。这种方法显示了广泛的官能团耐受性,适用于那些未活化的炔和含有氧化敏感基团的底物。通过EPR, FT-IR和NMR测量的机理研究表明,优异的催化性能源于炔和硝酸锌之间形成的配位中间体,通过离子偶极子相互作用被乙腈稳定。这种稳定性促进炔活化,促进氧原子从硝酸盐转移到CC键,并将硝酸盐还原为氮氧化物,氮氧化物随后作为自由基引发剂触发链式反应,加速CC键的氧化裂解,分子氧作为末端氧化剂。
{"title":"Metal nitrate in acetonitrile-driven aerobic oxidative cleavage of alkynes to carboxylic acids under mild conditions","authors":"Chao Xie, Zejun Liu, Huichao Wang, Qidong Hou, Hengli Qian, Zhiwei Jiang, Meiting Ju","doi":"10.1016/j.jcat.2026.116719","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116719","url":null,"abstract":"C<ce:glyph name=\"tbnd\"></ce:glyph>C bond cleavage in alkynes provides a powerful strategy for the functional group transformation of alkyne compounds, but it is challenging to balance reactivity and selectivity due to its high bond dissociation energy and inherently complex reaction pathways. In this work, we report the use of commercially available nitrates in acetonitrile for the mild aerobic oxidative cleavage of the alkyne C<ce:glyph name=\"tbnd\"></ce:glyph>C bonds, resulting in the formation of carboxylic acids with good to excellent yields. This approach demonstrates broad functional group tolerance, applicable to those unactivated alkynes and substrates containing oxidation-sensitive groups. Mechanistic studies using EPR, FT-IR, and NMR measurements reveal that the excellent catalytic property arises from the formation of coordination intermediates between the alkyne and zinc nitrate, stabilized by acetonitrile through ion–dipole interactions. This stabilization promotes alkyne activation, facilitates the oxygen atom transfer (OAT) from nitrate to the C<ce:glyph name=\"tbnd\"></ce:glyph>C bond and reduces the nitrate to nitrogen oxides, which then act as free-radical initiators to trigger a chain reaction and accelerate the oxidative cleavage of the C<ce:glyph name=\"tbnd\"></ce:glyph>C bond, with molecular oxygen serving as the terminal oxidant.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"73 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056546","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}
引用次数: 0
BEA zeolite encapsulated defective Co sites for solvent- and additive-free N-alkylation of amines with aromatic alcohols BEA沸石包覆有缺陷的Co位点,用于无溶剂和无添加剂的胺与芳香醇的n -烷基化
IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-23 DOI: 10.1016/j.jcat.2026.116713
Meng Xu , Zhongliang Tang , Yue Wu , Menglin Xie , Biao Meng , Xiao Chi , Xiaojiang Yu , Xiaoling Liu , Shibo Xi , Yu Zhou , Jun Wang
Hydrogen borrowing amination provides a sustainable alcohol-based N-alkylation method for the amine synthesis and functionalization, yet the development of non-noble metal catalysts that are effective under additive- and solvent-free conditions remains a huge challenge. Herein, we report a Cobalt (Co)-containing zeolite, Co@Beta, prepared by directly encapsulating defect Co sites within BEA framework via an acid co-hydrolysis route. Co@Beta shows excellent catalytic performance in the N-alkylation of benzyl alcohol with aniline, achieving > 92% yield and a turnover frequency (TOF) of 466 h−1 without external solvent or additive. The catalyst is stable during the recycling amination and extendable to the amination between various aromatic alcohols and amines. In situ spectroscopic analysis, theoretical calculations, as well as step-by-step comparison with post-loaded analogues, reveal that defect Co sites within Co@Beta are active centers, thereby lowering the energy barrier for the rate-determining dehydrogenation step and underpinning the superior amination performance.
借氢胺化为胺的合成和功能化提供了一种可持续的醇基n-烷基化方法,但开发在无添加剂和无溶剂条件下有效的非贵金属催化剂仍然是一个巨大的挑战。在此,我们报告了一种含钴(Co)的沸石,Co@Beta,通过酸共水解途径直接封装在BEA框架内的缺陷Co位点。Co@Beta在苯甲醇与苯胺的n -烷基化反应中表现出优异的催化性能,产率达到92%,周转频率(TOF)为466 h−1,无需外源溶剂或添加剂。该催化剂在循环胺化过程中稳定,可扩展到各种芳香醇与胺之间的胺化反应。原位光谱分析、理论计算以及与后加载类似物的逐步比较表明,Co@Beta中的缺陷Co位点是活性中心,从而降低了决定速率脱氢步骤的能量势垒,并支撑了优越的胺化性能。
{"title":"BEA zeolite encapsulated defective Co sites for solvent- and additive-free N-alkylation of amines with aromatic alcohols","authors":"Meng Xu ,&nbsp;Zhongliang Tang ,&nbsp;Yue Wu ,&nbsp;Menglin Xie ,&nbsp;Biao Meng ,&nbsp;Xiao Chi ,&nbsp;Xiaojiang Yu ,&nbsp;Xiaoling Liu ,&nbsp;Shibo Xi ,&nbsp;Yu Zhou ,&nbsp;Jun Wang","doi":"10.1016/j.jcat.2026.116713","DOIUrl":"10.1016/j.jcat.2026.116713","url":null,"abstract":"<div><div>Hydrogen borrowing amination provides a sustainable alcohol-based N-alkylation method for the amine synthesis and functionalization, yet the development of non-noble metal catalysts that are effective under additive- and solvent-free conditions remains a huge challenge. Herein, we report a Cobalt (Co)-containing zeolite, Co@Beta, prepared by directly encapsulating defect Co sites within BEA framework <em>via</em> an acid co-hydrolysis route. Co@Beta shows excellent catalytic performance in the N-alkylation of benzyl alcohol with aniline, achieving &gt; 92% yield and a turnover frequency (TOF) of 466 h<sup>−1</sup> without external solvent or additive. The catalyst is stable during the recycling amination and extendable to the amination between various aromatic alcohols and amines. <em>In situ</em> spectroscopic analysis, theoretical calculations, as well as step-by-step comparison with post-loaded analogues, reveal that defect Co sites within Co@Beta are active centers, thereby lowering the energy barrier for the rate-determining dehydrogenation step and underpinning the superior amination performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116713"},"PeriodicalIF":6.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033865","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}
引用次数: 0
Inducing polar electric fields via molecular unit symmetry breaking for boosting photocatalysis 通过分子单元对称破缺诱导极性电场促进光催化
IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-23 DOI: 10.1016/j.jcat.2026.116711
Xiaoyu Nie , Chengyi Ou , Jingwen Liang , Chenglong Ru , Xiaobo Pan , Sibo Wang , Zhi-An Lan
The separation and transport efficiency of photogenerated charge carriers are critical factors determining the photocatalytic performance of semiconductors. However, the lack of a direct and effective driving force for charge separation leads to rapid recombination of most photogenerated carriers within the bulk or on the surface of photocatalysts, severely limiting their output efficiency. Constructing an internal polarization electric field to drive the directional migration of charges and suppress carrier recombination has been demonstrated as an effective strategy. In this study, we designed and synthesized two conjugated polymers with distinct symmetries via a local π-skeleton modulation strategy of molecular units. We systematically clarified the regulatory mechanism underlying the disruption of molecular structural unit symmetry on the photocatalytic charge transport process. Both experimental results and theoretical calculations demonstrated that the breaking of molecular unit symmetry induces an internal electric field within the photocatalyst, which provides an intrinsic driving force for the directional migration and rapid accumulation of electrons. This process establishes a continuous π-electron delocalization channel, creating a “charge superhighway”, while reducing the exciton binding energy (Eb) to significantly suppress carrier recombination, thereby substantially enhancing the photocatalytic performance. This study demonstrates the polarization effect caused by the disruption of molecular unit symmetry, which can amplify the electric field strength to optimize charge separation and provide a design option for high-efficiency organic photocatalysts.
光生载流子的分离和输运效率是决定半导体光催化性能的关键因素。然而,由于缺乏直接有效的电荷分离驱动力,导致大多数光生载流子在体内或光催化剂表面快速重组,严重限制了它们的输出效率。构建内部极化电场来驱动电荷的定向迁移和抑制载流子的复合是一种有效的策略。在本研究中,我们通过分子单元的局部π-骨架调制策略,设计并合成了两种具有不同对称性的共轭聚合物。我们系统地阐明了光催化电荷传输过程中分子结构单元对称性破坏的调控机制。实验结果和理论计算均表明,分子单元对称性的破坏在光催化剂内部产生了一个内部电场,为电子的定向迁移和快速积累提供了内在动力。该过程建立了连续的π-电子离域通道,形成了“电荷高速公路”,同时降低激子结合能(Eb),显著抑制载流子复合,从而大大提高了光催化性能。本研究证明了分子单元对称破坏引起的极化效应,可以放大电场强度以优化电荷分离,为高效有机光催化剂的设计提供了一种选择。
{"title":"Inducing polar electric fields via molecular unit symmetry breaking for boosting photocatalysis","authors":"Xiaoyu Nie ,&nbsp;Chengyi Ou ,&nbsp;Jingwen Liang ,&nbsp;Chenglong Ru ,&nbsp;Xiaobo Pan ,&nbsp;Sibo Wang ,&nbsp;Zhi-An Lan","doi":"10.1016/j.jcat.2026.116711","DOIUrl":"10.1016/j.jcat.2026.116711","url":null,"abstract":"<div><div>The separation and transport efficiency of photogenerated charge carriers are critical factors determining the photocatalytic performance of semiconductors. However, the lack of a direct and effective driving force for charge separation leads to rapid recombination of most photogenerated carriers within the bulk or on the surface of photocatalysts, severely limiting their output efficiency. Constructing an internal polarization electric field to drive the directional migration of charges and suppress carrier recombination has been demonstrated as an effective strategy. In this study, we designed and synthesized two conjugated polymers with distinct symmetries via a local π-skeleton modulation strategy of molecular units. We systematically clarified the regulatory mechanism underlying the disruption of molecular structural unit symmetry on the photocatalytic charge transport process. Both experimental results and theoretical calculations demonstrated that the breaking of molecular unit symmetry induces an internal electric field within the photocatalyst, which provides an intrinsic driving force for the directional migration and rapid accumulation of electrons. This process establishes a continuous π-electron delocalization channel, creating a “charge superhighway”, while reducing the exciton binding energy (<em>E</em><sub>b</sub>) to significantly suppress carrier recombination, thereby substantially enhancing the photocatalytic performance. This study demonstrates the polarization effect caused by the disruption of molecular unit symmetry, which can amplify the electric field strength to optimize charge separation and provide a design option for high-efficiency organic photocatalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116711"},"PeriodicalIF":6.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033864","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}
引用次数: 0
Deep hydrogenation of nitrite intermediate with H-radicals for promoted nitrate reduction to ammonia 亚硝酸盐中间体与h自由基深度加氢促进硝酸盐还原为氨
IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-01-23 DOI: 10.1016/j.jcat.2026.116712
Chunling Zhang, Shuangshuang Yu, Shujie Shen, Huimin Dan, Wei Wu, Jieyuan Li, Fan Dong
The treatment of nitrate (NO3) pollutants is of critical importance for both human health and sustainable environmental development. The efficient conversion of low-concentration NO3 is mainly challenged by the competing hydrogen evolution side reactions and the lack of efficient hydrogen sources for deep hydrogenation. Here, we report a redox-enhanced photocatalytic system by constructing spatially separated CuxO nanoclusters (CuxO NCs) and oxygen vacancies (OVs) as dual active sites on a TiO2 nanotube support. CuxO NCs, as electron enrichment centers, significantly enhance the adsorption and activation capabilities for NO3, thereby enabling NO3 to be activated into the key intermediate nitrite (NO2). OVs, as efficient hole-trapping sites, accelerate the oxidation half-reaction, promoting the generation of highly reactive hydrogen radicals (H). Most importantly, the directional addition of the H to NO2 facilitates its deep reduction via a H-mediated pathway, leading to the highly selective generation of ammonia (NH3). Almost 100 % of the NO3 conversion ratio and a competitive NH3 selectivity (98.3 ± 0.16 %) are achieved in this system. This study highlights the critical roles of NO3 activation and H in efficient NO3 conversion, providing an innovative strategy for the resource utilization of NO3-contaminated wastewater.
Environmental Implication: A redox-enhanced photocatalytic system is constructed to enable efficient activation of NO3 to NO2 and subsequently H-mediated hydrogenation. As a result, nearly complete NO3 removal ratio (∼100 %) with high selectivity toward NH3 (98.3 ± 0.16 %) is achieved. This study provides insights and guidance for the efficient conversion and resource utilization of low-concentration NO3, significantly advancing the application of photocatalytic technology in environmental remediation and resource recovery. It also offers support for the establishment of a sustainable nitrogen cycle system.
硝酸盐(NO3−)污染物的处理对人类健康和环境可持续发展至关重要。低浓度NO3−的高效转化主要受到析氢副反应的竞争和缺乏有效的深度加氢氢源的挑战。在这里,我们报道了一个氧化还原增强的光催化系统,通过构建空间分离的CuxO纳米簇(CuxO NCs)和氧空位(OVs)作为TiO2纳米管载体上的双活性位点。CuxO NCs作为电子富集中心,显著增强了对NO3−的吸附和活化能力,从而使NO3−被活化为关键中间体亚硝酸盐(NO2−)。OVs作为有效的空穴捕获位点,加速氧化半反应,促进高活性氢自由基(H)的生成。最重要的是,H向NO2−的定向添加促进了其通过H介导的途径深度还原,导致氨(NH3)的高选择性生成。该体系的NO3−转化率几乎达到100%,NH3选择性达到98.3%±0.16%。该研究强调了NO3−活化和H在NO3−高效转化中的关键作用,为NO3−污染废水的资源化利用提供了创新策略。环境意义:构建了一个氧化还原增强的光催化系统,以实现NO3−到NO2−的有效活化和随后的h介导的氢化。结果表明,NO3−去除率几乎完全(~ 100%),对NH3具有高选择性(98.3%±0.16%)。该研究为低浓度NO3−的高效转化和资源化利用提供了见解和指导,显著推进了光催化技术在环境修复和资源回收中的应用。为建立可持续的氮循环系统提供了支持。
{"title":"Deep hydrogenation of nitrite intermediate with H-radicals for promoted nitrate reduction to ammonia","authors":"Chunling Zhang,&nbsp;Shuangshuang Yu,&nbsp;Shujie Shen,&nbsp;Huimin Dan,&nbsp;Wei Wu,&nbsp;Jieyuan Li,&nbsp;Fan Dong","doi":"10.1016/j.jcat.2026.116712","DOIUrl":"10.1016/j.jcat.2026.116712","url":null,"abstract":"<div><div>The treatment of nitrate (NO<sub>3</sub><sup>−</sup>) pollutants is of critical importance for both human health and sustainable environmental development. The efficient conversion of low-concentration NO<sub>3</sub><sup>−</sup> is mainly challenged by the competing hydrogen evolution side reactions and the lack of efficient hydrogen sources for deep hydrogenation. Here, we report a redox-enhanced photocatalytic system by constructing spatially separated Cu<sub>x</sub>O nanoclusters (Cu<sub>x</sub>O NCs) and oxygen vacancies (OVs) as dual active sites on a TiO<sub>2</sub> nanotube support. Cu<sub>x</sub>O NCs, as electron enrichment centers, significantly enhance the adsorption and activation capabilities for NO<sub>3</sub><sup>−</sup>, thereby enabling NO<sub>3</sub><sup>−</sup> to be activated into the key intermediate nitrite (NO<sub>2</sub><sup>−</sup>). OVs, as efficient hole-trapping sites, accelerate the oxidation half-reaction, promoting the generation of highly reactive hydrogen radicals (<sup><img></sup>H). Most importantly, the directional addition of the <sup><img></sup>H to NO<sub>2</sub><sup>−</sup> facilitates its deep reduction <em>via</em> a <sup><img></sup>H-mediated pathway, leading to the highly selective generation of ammonia (NH<sub>3</sub>). Almost 100 % of the NO<sub>3</sub><sup>−</sup> conversion ratio and a competitive NH<sub>3</sub> selectivity (98.3 ± 0.16 %) are achieved in this system. This study highlights the critical roles of NO<sub>3</sub><sup>−</sup> activation and <sup><img></sup>H in efficient NO<sub>3</sub><sup>−</sup> conversion, providing an innovative strategy for the resource utilization of NO<sub>3</sub><sup>−</sup>-contaminated wastewater.</div><div><strong>Environmental Implication:</strong> A redox-enhanced photocatalytic system is constructed to enable efficient activation of NO<sub>3</sub><sup>−</sup> to NO<sub>2</sub><sup>−</sup> and subsequently <sup><img></sup>H-mediated hydrogenation. As a result, nearly complete NO<sub>3</sub><sup>−</sup> removal ratio (∼100 %) with high selectivity toward NH<sub>3</sub> (98.3 ± 0.16 %) is achieved. This study provides insights and guidance for the efficient conversion and resource utilization of low-concentration NO<sub>3</sub><sup>−</sup>, significantly advancing the application of photocatalytic technology in environmental remediation and resource recovery. It also offers support for the establishment of a sustainable nitrogen cycle system.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116712"},"PeriodicalIF":6.5,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033938","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}
引用次数: 0
期刊
Journal of Catalysis
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1