The development of a highly efficient and stable metal-free solid base catalyst for the Knoevenagel reaction remains a significant challenge. In this study, activated carbon is selected as support material to develop a new base catalyst due to its excellent chemical stability. A novel surface chloromethylation method is applied to modify the activated carbon surface, followed by covalent grafting of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), resulting in a highly effective solid organic base catalyst. A continuous platform based on a micro-packed bed reactor has been optimized for the Knoevenagel reaction. The system achieves excellent space-time yields (19129.4 <span><span style=""><math><mrow is="true"><msub is="true"><mi is="true" mathvariant="normal">g</mi><mrow is="true"><mi is="true" mathvariant="normal">P</mi><mi is="true" mathvariant="normal">r</mi><mi is="true" mathvariant="normal">o</mi><mspace is="true" width="0.166667em"></mspace></mrow></msub><msubsup is="true"><mrow is="true"><mi is="true" mathvariant="normal">k</mi><mi is="true" mathvariant="normal">g</mi></mrow><mrow is="true"><mi is="true" mathvariant="normal">c</mi><mi is="true" mathvariant="normal">a</mi><mi is="true" mathvariant="normal">t</mi></mrow><mrow is="true"><mo is="true">-</mo><mn is="true">1</mn></mrow></msubsup><mspace is="true" width="0.166667em"></mspace><msup is="true"><mrow is="true"><mi is="true" mathvariant="normal">h</mi></mrow><mrow is="true"><mo is="true">-</mo><mn is="true">1</mn></mrow></msup></mrow></math></span><span style="font-size: 90%; display: inline-block;" tabindex="0"></span><script type="math/mml"><math><mrow is="true"><msub is="true"><mi mathvariant="normal" is="true">g</mi><mrow is="true"><mi mathvariant="normal" is="true">P</mi><mi mathvariant="normal" is="true">r</mi><mi mathvariant="normal" is="true">o</mi><mspace width="0.166667em" is="true"></mspace></mrow></msub><msubsup is="true"><mrow is="true"><mi mathvariant="normal" is="true">k</mi><mi mathvariant="normal" is="true">g</mi></mrow><mrow is="true"><mi mathvariant="normal" is="true">c</mi><mi mathvariant="normal" is="true">a</mi><mi mathvariant="normal" is="true">t</mi></mrow><mrow is="true"><mo is="true">-</mo><mn is="true">1</mn></mrow></msubsup><mspace width="0.166667em" is="true"></mspace><msup is="true"><mrow is="true"><mi mathvariant="normal" is="true">h</mi></mrow><mrow is="true"><mo is="true">-</mo><mn is="true">1</mn></mrow></msup></mrow></math></script></span>) and demonstrates a broad substrate scope. The solid organic base catalyst exhibits a turnover frequency (<em>TOF</em>) exceeding 140 <span><span style=""><math><msup is="true"><mrow is="true"><mi is="true" mathvariant="normal">h</mi></mrow><mrow is="true"><mo is="true">-</mo><mn is="true">1</mn></mrow></msup></math></span><span style="font-size: 90%; display: inline-block;" tabindex="0"></span><script type="math/mml"><math><msup is="true"><mrow is="true"><mi mathvariant="normal" is="true">h</mi></mrow><mrow is="true"><
{"title":"TBD-grafted activated carbon as an efficient solid base catalyst for continuous Knoevenagel reaction","authors":"Yi Chen, Xueqing Ma, Chenghao Zhang, Bingqi Xie, Wangyang Ma, Jisong Zhang","doi":"10.1016/j.jcat.2025.116156","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116156","url":null,"abstract":"The development of a highly efficient and stable metal-free solid base catalyst for the Knoevenagel reaction remains a significant challenge. In this study, activated carbon is selected as support material to develop a new base catalyst due to its excellent chemical stability. A novel surface chloromethylation method is applied to modify the activated carbon surface, followed by covalent grafting of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), resulting in a highly effective solid organic base catalyst. A continuous platform based on a micro-packed bed reactor has been optimized for the Knoevenagel reaction. The system achieves excellent space-time yields (19129.4 <span><span style=\"\"><math><mrow is=\"true\"><msub is=\"true\"><mi is=\"true\" mathvariant=\"normal\">g</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">P</mi><mi is=\"true\" mathvariant=\"normal\">r</mi><mi is=\"true\" mathvariant=\"normal\">o</mi><mspace is=\"true\" width=\"0.166667em\"></mspace></mrow></msub><msubsup is=\"true\"><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">k</mi><mi is=\"true\" mathvariant=\"normal\">g</mi></mrow><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">c</mi><mi is=\"true\" mathvariant=\"normal\">a</mi><mi is=\"true\" mathvariant=\"normal\">t</mi></mrow><mrow is=\"true\"><mo is=\"true\">-</mo><mn is=\"true\">1</mn></mrow></msubsup><mspace is=\"true\" width=\"0.166667em\"></mspace><msup is=\"true\"><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">h</mi></mrow><mrow is=\"true\"><mo is=\"true\">-</mo><mn is=\"true\">1</mn></mrow></msup></mrow></math></span><span style=\"font-size: 90%; display: inline-block;\" tabindex=\"0\"></span><script type=\"math/mml\"><math><mrow is=\"true\"><msub is=\"true\"><mi mathvariant=\"normal\" is=\"true\">g</mi><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">P</mi><mi mathvariant=\"normal\" is=\"true\">r</mi><mi mathvariant=\"normal\" is=\"true\">o</mi><mspace width=\"0.166667em\" is=\"true\"></mspace></mrow></msub><msubsup is=\"true\"><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">k</mi><mi mathvariant=\"normal\" is=\"true\">g</mi></mrow><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">c</mi><mi mathvariant=\"normal\" is=\"true\">a</mi><mi mathvariant=\"normal\" is=\"true\">t</mi></mrow><mrow is=\"true\"><mo is=\"true\">-</mo><mn is=\"true\">1</mn></mrow></msubsup><mspace width=\"0.166667em\" is=\"true\"></mspace><msup is=\"true\"><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">h</mi></mrow><mrow is=\"true\"><mo is=\"true\">-</mo><mn is=\"true\">1</mn></mrow></msup></mrow></math></script></span>) and demonstrates a broad substrate scope. The solid organic base catalyst exhibits a turnover frequency (<em>TOF</em>) exceeding 140 <span><span style=\"\"><math><msup is=\"true\"><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">h</mi></mrow><mrow is=\"true\"><mo is=\"true\">-</mo><mn is=\"true\">1</mn></mrow></msup></math></span><span style=\"font-size: 90%; display: inline-block;\" tabindex=\"0\"></span><script type=\"math/mml\"><math><msup is=\"true\"><mrow is=\"true\"><mi mathvariant=\"normal\" is=\"true\">h</mi></mrow><mrow is=\"true\"><","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"32 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862711","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 : 2025-04-22DOI: 10.1016/j.jcat.2025.116149
Marvi Kaushik, Tuhin S. Khan, M. Ali Haider, Divesh Bhatia
Density Functional Theory (DFT) simulations are performed to understand the impact of zeolite framework on the operating cycle of NO adsorption and desorption in Pd-based passive NOx adsorbers. The binding energy on all sites exhibits the trend: BEA > ZSM-5 > CHA, which is consistent with reported trends in the NOx desorption temperatures. Independent of the zeolite framework, NO binds strongly on Pd1+ site, whereas its binding on Pd(II) sites (Pd2+, [PdOH]+, dimeric Pd) is considerably weaker. However, the binding strength on Pd1+ and Pd2+ sites is similar in ZSM-5 and BEA. The free energy of activation for the reduction of Pd(II) species by NO is dependent on the zeolite framework. NO oxidation on [Pd-O-Pd]2+ has a low free energy barrier in ZSM-5 (29 kJ/mol) but exhibits the highest reaction barrier in CHA (77 kJ/mol). Further, the reoxidation of Pd1+ to [Pd-O-Pd]2+ is facile in Ferrierite (FER) but has a high free energy barrier in Chabazite (CHA). A kinetic model is developed for Pd/CHA and Pd/BEA which predicts a single desorption peak for CHA and two desorption peaks for BEA. The site-specific NO binding energy trends and the energetics of interconversion between sites result in differences in the NOx adsorption-desorption characteristics on different zeolite frameworks. The presence of H2O decreases the NO binding strength on all Pd sites except Pd2+ in FER and [PdOH]+ in CHA. CO preferentially reduces the Pd(II) species when both CO and NO are co-adsorbed on [PdOH]+[PdOH]+ with BEA exhibiting the lowest barrier.
{"title":"Effect of zeolite framework on the NO operating cycle in Pd-based passive NOx adsorbers","authors":"Marvi Kaushik, Tuhin S. Khan, M. Ali Haider, Divesh Bhatia","doi":"10.1016/j.jcat.2025.116149","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116149","url":null,"abstract":"Density Functional Theory (DFT) simulations are performed to understand the impact of zeolite framework on the operating cycle of NO adsorption and desorption in Pd-based passive NO<sub>x</sub> adsorbers. The binding energy on all sites exhibits the trend: BEA > ZSM-5 > CHA, which is consistent with reported trends in the NO<sub>x</sub> desorption temperatures. Independent of the zeolite framework, NO binds strongly on Pd<sup>1+</sup> site, whereas its binding on Pd(II) sites (Pd<sup>2+</sup>, [PdOH]<sup>+</sup>, dimeric Pd) is considerably weaker. However, the binding strength on Pd<sup>1+</sup> and Pd<sup>2+</sup> sites is similar in ZSM-5 and BEA. The free energy of activation for the reduction of Pd(II) species by NO is dependent on the zeolite framework. NO oxidation on [Pd-O-Pd]<sup>2+</sup> has a low free energy barrier in ZSM-5 (29 kJ/mol) but exhibits the highest reaction barrier in CHA (77 kJ/mol). Further, the reoxidation of Pd<sup>1+</sup> to [Pd-O-Pd]<sup>2+</sup> is facile in Ferrierite (FER) but has a high free energy barrier in Chabazite (CHA). A kinetic model is developed for Pd/CHA and Pd/BEA which predicts a single desorption peak for CHA and two desorption peaks for BEA. The site-specific NO binding energy trends and the energetics of interconversion between sites result in differences in the NO<sub>x</sub> adsorption-desorption characteristics on different zeolite frameworks. The presence of H<sub>2</sub>O decreases the NO binding strength on all Pd sites except Pd<sup>2+</sup> in FER and [PdOH]<sup>+</sup> in CHA. CO preferentially reduces the Pd(II) species when both CO and NO are co-adsorbed on [PdOH]<sup>+</sup>[PdOH]<sup>+</sup> with BEA exhibiting the lowest barrier.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"19 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862705","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}
Contact-electro-catalysis (CEC), utilizing electron transfer during contact electrification (CE) to accelerate chemical reactions, has garnered extensive attention as an emerging field. However, how many activated electrons produced during CE participate in the CEC are necessary to be quantitatively analyzed for further improving the CEC reaction. Hence, we introduce an analytical method for investigating CE-to-CEC conversion at various temperatures and ultrasonic conditions, as well as a quantitative metric of the amount of activated electrons in a single charge transfer cycle for evaluating the performance of different CEC catalysts. This study elucidates the proportion of electrons involved in CEC during CE, which provides insights on the transition from CE to CEC, and facilitates further optimization researches for CEC.
接触电催化（CEC）是利用接触电化（CE）过程中的电子转移来加速化学反应，作为一个新兴领域受到广泛关注。然而，究竟有多少在接触电化过程中产生的活化电子参与了接触电催化反应，还需要进行定量分析，以进一步改进接触电催化反应。因此，我们介绍了一种在不同温度和超声波条件下研究 CE 到 CEC 转化的分析方法，以及单次电荷转移循环中活化电子数量的定量指标，用于评估不同 CEC 催化剂的性能。这项研究阐明了在 CE 过程中参与 CEC 的电子比例，从而深入了解了从 CE 到 CEC 的转变过程，并有助于进一步优化 CEC 的研究。
{"title":"Quantified analysis on the conversion from contact electrification to contact-electro-catalysis and the performance of contact-electro-catalysts","authors":"Xuanli Dong, Ziming Wang, Yu Hou, Tingyu Wang, Fu-Jie Lv, Wei Tang","doi":"10.1016/j.jcat.2025.116153","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116153","url":null,"abstract":"Contact-electro-catalysis (CEC), utilizing electron transfer during contact electrification (CE) to accelerate chemical reactions, has garnered extensive attention as an emerging field. However, how many activated electrons produced during CE participate in the CEC are necessary to be quantitatively analyzed for further improving the CEC reaction. Hence, we introduce an analytical method for investigating CE-to-CEC conversion at various temperatures and ultrasonic conditions, as well as a quantitative metric of the amount of activated electrons in a single charge transfer cycle for evaluating the performance of different CEC catalysts. This study elucidates the proportion of electrons involved in CEC during CE, which provides insights on the transition from CE to CEC, and facilitates further optimization researches for CEC.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"51 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862765","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 : 2025-04-21DOI: 10.1016/j.jcat.2025.116162
Xue Jia, Tianyi Wang, Di Zhang, Xuan Wang, Heng Liu, Liang Zhang, Hao Li
The integration of data science into electrocatalysis has revolutionized the discovery of high-performance catalysts for sustainable energy applications. To emphasize the role of data science and guide future research in electrocatalyst design, this mini-review traces the evolution from low-dimensional data science—rooted in density functional theory (DFT) descriptors such as d-band center and binding/adsorption energies—to high-dimensional analytics powered by large-scale computational datasets and machine learning (ML). First, DFT-derived parameters establish predictive volcano models for various electrochemical reactions, linking atomic-scale descriptors to macroscopic performance within the framework of low-dimensional data science. Meanwhile, with the development of large-scale datasets, ML deciphers complex structure–property relationships, accelerating the design of promising electrocatalysts. Additionally, machine learning potentials (MLPs) bridge quantum precision and scalability, not only accelerating thermodynamic adsorption energy calculations but also enabling simulations of dynamic catalytic mechanisms more efficiently. Finally, we discuss emerging opportunities to deepen data science’s impact. This mini-review highlights the transformative role of data science in bridging theoretical insights, computational efficiency, and experimental validation, ultimately accelerating the design of next-generation electrocatalysts for a sustainable energy future.
{"title":"Advancing electrocatalyst discovery through the lens of data science: State of the art and perspectives☆","authors":"Xue Jia, Tianyi Wang, Di Zhang, Xuan Wang, Heng Liu, Liang Zhang, Hao Li","doi":"10.1016/j.jcat.2025.116162","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116162","url":null,"abstract":"The integration of data science into electrocatalysis has revolutionized the discovery of high-performance catalysts for sustainable energy applications. To emphasize the role of data science and guide future research in electrocatalyst design, this mini-review traces the evolution from low-dimensional data science—rooted in density functional theory (DFT) descriptors such as <em>d</em>-band center and binding/adsorption energies—to high-dimensional analytics powered by large-scale computational datasets and machine learning (ML). First, DFT-derived parameters establish predictive volcano models for various electrochemical reactions, linking atomic-scale descriptors to macroscopic performance within the framework of low-dimensional data science. Meanwhile, with the development of large-scale datasets, ML deciphers complex structure–property relationships, accelerating the design of promising electrocatalysts. Additionally, machine learning potentials (MLPs) bridge quantum precision and scalability, not only accelerating thermodynamic adsorption energy calculations but also enabling simulations of dynamic catalytic mechanisms more efficiently. Finally, we discuss emerging opportunities to deepen data science’s impact. This mini-review highlights the transformative role of data science in bridging theoretical insights, computational efficiency, and experimental validation, ultimately accelerating the design of next-generation electrocatalysts for a sustainable energy future.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"32 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858092","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 utilization of sustainable lignocellulosic biomass for the production of high-value products could potentially solve the intensive reliance on fossil fuels. 2,5-furandicarboxylic acid (FDCA), obtained from 5-hydroxymethylfurfural (HMF) oxidation, is a significant precursor for biomass converted high-value chemicals. Nowadays, the rational design of pre-catalysts via electrochemical self-reconstruction provides an opportunity to design efficient catalysts for electrooxidation process. In this study, we developed a pre-catalyst consisting of nanoscale cubic NiFePBA anchored on Ni(OH)2. After electrochemical reconstruction, it demonstrated superior HMF oxidation reaction (HMFOR) performance. The results demonstrate that the electrochemical self-reconstruction process converts nanoscale cubic NiFePBA into nanosheeted metal oxyhydroxide, resulting in the formation of an oxygen defect-rich heterostructure with Ni(OH)2. This reconstruction process also enhance the electrochemically active surface area, thereby increasing the number of active sites. The combined effect of increased active sites and oxygen defects significantly enhances the HMF adsorption and the HMFOR activity. In situ electrochemical impedance spectroscopy further reveals that the reconstructed NiFePBA/Ni(OH)2-R exhibits accelerated reaction kinetics and reduced reaction potential during the electrocatalytic oxidation of HMF. The NiFePBA/Ni(OH)2 -R catalyst exhibited exceptional electrochemical performance, achieving a high current density of 50 mA·cm–2 at a relatively low potential of 1.43 V vs. RHE. This performance is characterized by a remarkable 99.1 % conversion of HMF, 98.5 % selectivity for FDCA, and a Faradaic efficiency of 94.2 %. This study offers valuable insights for the development of high-performance HMFOR electrocatalysts.
{"title":"An efficient catalyst from electrochemical self-reconstruction of NiFePBA/Ni(OH)2 for 5-hydroxymethylfurfural electrooxidation to produce high-valued 2,5-furandicarboxylic acid","authors":"Xuhui Chen, Hao Liu, Lei Chen, Wei Xiong, Yuqi Liu, Xiujuan Sun, Fang Hao","doi":"10.1016/j.jcat.2025.116159","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116159","url":null,"abstract":"The utilization of sustainable lignocellulosic biomass for the production of high-value products could potentially solve the intensive reliance on fossil fuels. 2,5-furandicarboxylic acid (FDCA), obtained from 5-hydroxymethylfurfural (HMF) oxidation, is a significant precursor for biomass converted high-value chemicals. Nowadays, the rational design of pre-catalysts <em>via</em> electrochemical self-reconstruction provides an opportunity to design efficient catalysts for electrooxidation process. In this study, we developed a pre-catalyst consisting of nanoscale cubic NiFePBA anchored on Ni(OH)<sub>2</sub>. After electrochemical reconstruction, it demonstrated superior HMF oxidation reaction (HMFOR) performance. The results demonstrate that the electrochemical self-reconstruction process converts nanoscale cubic NiFePBA into nanosheeted metal oxyhydroxide, resulting in the formation of an oxygen defect-rich heterostructure with Ni(OH)<sub>2</sub>. This reconstruction process also enhance the electrochemically active surface area, thereby increasing the number of active sites. The combined effect of increased active sites and oxygen defects significantly enhances the HMF adsorption and the HMFOR activity. <em>In situ</em> electrochemical impedance spectroscopy further reveals that the reconstructed NiFePBA/Ni(OH)<sub>2</sub>-R exhibits accelerated reaction kinetics and reduced reaction potential during the electrocatalytic oxidation of HMF. The NiFePBA/Ni(OH)<sub>2</sub> -R catalyst exhibited exceptional electrochemical performance, achieving a high current density of 50 mA·cm<sup>–2</sup> at a relatively low potential of 1.43 V vs. RHE. This performance is characterized by a remarkable 99.1 % conversion of HMF, 98.5 % selectivity for FDCA, and a Faradaic efficiency of 94.2 %. This study offers valuable insights for the development of high-performance HMFOR electrocatalysts.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"12 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858130","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 rhenium(I)-bipyridine complex (Re-bpy) has been reported to be a very active photocatalyst to stabilize the *CO species in CO2 reduction, and the copper-porphyrinic triazine framework Cu-PTF was found to be a very good relay partner and cooperator in facilitating the C−C coupling process to generate C2H4. To unravel the mechanism of reduction of CO2 to C1 and C2 products and how such two catalysts synergistically promote C−C coupling, we conducted density functional theory (DFT) calculations. The most favorable mechanism comprises the following key steps: CO2 activation by Re-bpy, formation of Re − CO species, proton-coupled electron transfer (PCET) to form Re − CHO species, synergistic coupling between Re − CHO and Cu − CO to form Cu − CO − CHO − Re intermediate, the PCET to form resting state Cu − CHO − CH2 − Re intermediate, another PCET to generate Cu − CHOH − CH2 − Re, PCET and elimination of H2O and dissociation to yield C2H4. Our DFT calculations provides insights into the catalytic pathways and the cooperative interactions between the two catalysts, paving the way for the development of more efficient catalytic systems for CO2 reduction reactions.
据报道，铼（I）-联吡啶络合物（Re-bpy）是一种非常活跃的光催化剂，可在二氧化碳还原过程中稳定*CO物种，而铜-卟啉三嗪框架Cu-PTF则是一种非常好的中继伙伴和合作者，可促进C-C偶联过程以生成C2H4。为了揭示 CO2 还原成 C1 和 C2 产物的机理，以及这两种催化剂如何协同促进 C-C 偶联，我们进行了密度泛函理论（DFT）计算。最有利的机制包括以下关键步骤：Re-bpy 活化 CO2、形成 Re - CO 物种、质子耦合电子转移 (PCET) 形成 Re - CHO 物种、Re - CHO 与 Cu - CO 协同耦合形成 Cu - CO - CHO - Re 中间体、PCET 形成静止态 Cu - CHO - CH2 - Re 中间体、另一个 PCET 生成 Cu - CHOH - CH2 - Re、PCET 和消除 H2O 并解离生成 C2H4。我们的 DFT 计算深入揭示了两种催化剂之间的催化途径和协同作用，为开发更高效的二氧化碳还原反应催化系统铺平了道路。
{"title":"Computational insights into the photocatalytic conversion of CO2 to C2H4 on synergistic dual sites in tandem rhenium-bipyridine/copper-porphyrinic system","authors":"Debo Ding, Xiahe Chen, Hongli Wu, Haimin Shen, Tengshuo Zhang, Keke Wang, Yun-Fang Yang, Yuan-Bin She","doi":"10.1016/j.jcat.2025.116144","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116144","url":null,"abstract":"The rhenium(I)-bipyridine complex (Re-bpy) has been reported to be a very active photocatalyst to stabilize the *CO species in CO<sub>2</sub> reduction, and the copper-porphyrinic triazine framework Cu-PTF was found to be a very good relay partner and cooperator in facilitating the C−C coupling process to generate C<sub>2</sub>H<sub>4</sub>. To unravel the mechanism of reduction of CO<sub>2</sub> to C<sub>1</sub> and C<sub>2</sub> products and how such two catalysts synergistically promote C−C coupling, we conducted density functional theory (DFT) calculations. The most favorable mechanism comprises the following key steps: CO<sub>2</sub> activation by Re-bpy, formation of Re − CO species, proton-coupled electron transfer (PCET) to form Re − CHO species, synergistic coupling between Re − CHO and Cu − CO to form Cu − CO − CHO − Re intermediate, the PCET to form resting state Cu − CHO − CH<sub>2</sub> − Re intermediate, another PCET to generate Cu − CHOH − CH<sub>2</sub> − Re, PCET and elimination of H<sub>2</sub>O and dissociation to yield C<sub>2</sub>H<sub>4</sub>. Our DFT calculations provides insights into the catalytic pathways and the cooperative interactions between the two catalysts, paving the way for the development of more efficient catalytic systems for CO<sub>2</sub> reduction reactions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"35 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853588","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}
Encapsulated catalysts have become a new strategy for catalysis in harsh reaction environments due to their unique structural and functional reorganization properties, and they have been widely applied in fields such as electrocatalysis, photocatalysis, and thermocatalysis. In strategies involving encapsulated catalysts, the optimization of electronic properties on the carbon layer surface to enhance reactivity while maintaining adequate encapsulation poses a challenge due to the trade-off between stability, poison resistance, and acid resistance against the performance of metal nanoparticles. Herein, an alloying strategy for Co-Ni bimetal was proposed, which achieves a delicate balance between catalyst activity and stability. Ni plays a pivotal role in promoting the formation of graphitized carbon and the construction of an effective encapsulation structure, thereby ensuring the stability of the catalyst. Co incorporation and alloying with Ni modulates the electronic state and D-band structure within the metallic core, effectively breaking the electronic cloud segregation barrier imposed by the carbon shell. This modulation notably enhances the efficiency of reactions. For the hydrogenation of p-CNB to p-CAN, Co2Ni8@C exhibits an extremely low apparent activation energy (53.40 KJ/mol), as well as > 99 % conversion and selectivity.
{"title":"Enhancing electron penetration through carbon shell of encapsulated catalysts by Co alloying for aromatic nitrobenzene hydrogenation","authors":"Wei He, Yanni Li, Qiuyuan Xiang, Xiyuan Zhang, Jiaxin Yu, Chaofan Ma, Yongyue Yao, Chunyu Yin, Yi Liu, Yebin Zhou, Xiaonian Li, Chunshan Lu","doi":"10.1016/j.jcat.2025.116150","DOIUrl":"10.1016/j.jcat.2025.116150","url":null,"abstract":"<div><div>Encapsulated catalysts have become a new strategy for catalysis in harsh reaction environments due to their unique structural and functional reorganization properties, and they have been widely applied in fields such as electrocatalysis, photocatalysis, and thermocatalysis. In strategies involving encapsulated catalysts, the optimization of electronic properties on the carbon layer surface to enhance reactivity while maintaining adequate encapsulation poses a challenge due to the trade-off between stability, poison resistance, and acid resistance against the performance of metal nanoparticles. Herein, an alloying strategy for Co-Ni bimetal was proposed, which achieves a delicate balance between catalyst activity and stability. Ni plays a pivotal role in promoting the formation of graphitized carbon and the construction of an effective encapsulation structure, thereby ensuring the stability of the catalyst. Co incorporation and alloying with Ni modulates the electronic state and D-band structure within the metallic core, effectively breaking the electronic cloud segregation barrier imposed by the carbon shell. This modulation notably enhances the efficiency of reactions. For the hydrogenation of <em>p</em>-CNB to <em>p</em>-CAN, Co<sub>2</sub>Ni<sub>8</sub>@C exhibits an extremely low apparent activation energy (53.40 KJ/mol), as well as > 99 % conversion and selectivity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116150"},"PeriodicalIF":6.5,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853863","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 : 2025-04-19DOI: 10.1016/j.jcat.2025.116146
Seongjun Lee, Jungwon Yun, Dasol Bae, Dohyeon Kim, Sung Bong Kang, Dohyung Kang, Minkyu Kim
The selective conversion of small alkanes into value-added products presents a significant challenge in catalysis due to the strong tendency toward complete oxidation. In this study, we employed DFT calculations and TPRS simulations to investigate ethane oxidation on the RhO2(1 1 0) surface. Our results demonstrate that the moderate reactivity of RhO2(1 1 0) enhances selectivity for ethylene production, positioning RhO2(1 1 0) as a promising catalyst for the selective oxidation of small alkanes and improved yields of value-added products. Extending beyond RhO2, we propose that highly reactive transition metal oxide surfaces may exhibit similar C2H4 desorption mechanisms involving C2H4 reformation-based desorption, as supported by comparisons with highly active IrO2. This insight suggests that catalytic strategies designed to facilitate reverse reactions for C2H4 reformation hold potential for boosting C2H4(g) production from C2H6 oxidation on active transition metal oxides.
{"title":"Selective conversion of ethane to value added products on RhO2(1 1 0): A DFT and microkinetic simulation study","authors":"Seongjun Lee, Jungwon Yun, Dasol Bae, Dohyeon Kim, Sung Bong Kang, Dohyung Kang, Minkyu Kim","doi":"10.1016/j.jcat.2025.116146","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116146","url":null,"abstract":"The selective conversion of small alkanes into value-added products presents a significant challenge in catalysis due to the strong tendency toward complete oxidation. In this study, we employed DFT calculations and TPRS simulations to investigate ethane oxidation on the RhO<sub>2</sub>(1<!-- --> <!-- -->1<!-- --> <!-- -->0) surface. Our results demonstrate that the moderate reactivity of RhO<sub>2</sub>(1<!-- --> <!-- -->1<!-- --> <!-- -->0) enhances selectivity for ethylene production, positioning RhO<sub>2</sub>(1<!-- --> <!-- -->1<!-- --> <!-- -->0) as a promising catalyst for the selective oxidation of small alkanes and improved yields of value-added products. Extending beyond RhO<sub>2</sub>, we propose that highly reactive transition metal oxide surfaces may exhibit similar C<sub>2</sub>H<sub>4</sub> desorption mechanisms involving C<sub>2</sub>H<sub>4</sub> reformation-based desorption, as supported by comparisons with highly active IrO<sub>2</sub>. This insight suggests that catalytic strategies designed to facilitate reverse reactions for C<sub>2</sub>H<sub>4</sub> reformation hold potential for boosting C<sub>2</sub>H<sub>4</sub>(g) production from C<sub>2</sub>H<sub>6</sub> oxidation on active transition metal oxides.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"28 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853867","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}
Heterogeneously catalytic depolymerization of lignin into value-added biochemicals are imperative, yet challengeable by the limited mass transport of lignin and the non-ideal spatial distributions of active sites in catalysts. Herein, a series of polycrystalline materials with Cu and Fe oxides encapsulated in hierarchical hollow nano silicalite (Cux-Fey@HhNS) were designed for step-by-step oxidative conversion of lignin into diethyl meleate (DEM). 92.0 % conversion of lignin with an exceptional DEM yield of 31.2 wt% and selectivity of 70.7 % was achieved at 150 °C for 24 h using Cu2.5-Fe2.2@HhNS. A series of controlled experiments and characterization showed clearly that the superior performance in DEM production was attributed to the enhanced tandem processes of lignin Cα-Cβ bonds deconstruction by framework Cu2+, subsequently aromatic ring-cleavage by the isolated framework Fe3+, and the well-balanced micro-/mesoporosity ratio of Cux-Fey@HhNS facilitates the diffusion of lignin macromolecules/products, contributing to the excellent DEM yield and selectivity as well. Further mechanistic investigation illustrated that the process proceeds via a single electron transfer pathway. Consequently, this work provides new insights into lignin valorization to bulk chemicals, paving the way for biomass-derived recyclable polymeric materials as sustainable alternative to traditional petroleum-based routes.
{"title":"Hierarchical hollow silicalite encapsulated Cu-Fe oxides for selectively oxidative depolymerization of lignin to diethyl meleate","authors":"Lixia Li, Juanhua Kong, Jinxing Long, Zhengping Cai, Qiang Zeng, Kejia Wu, Yingying Zhan, Sijie Liu, Hongyan He, Xuehui Li","doi":"10.1016/j.jcat.2025.116157","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116157","url":null,"abstract":"Heterogeneously catalytic depolymerization of lignin into value-added biochemicals are imperative, yet challengeable by the limited mass transport of lignin and the non-ideal spatial distributions of active sites in catalysts. Herein, a series of polycrystalline materials with Cu and Fe oxides encapsulated in hierarchical hollow nano silicalite (Cu<em><sub>x</sub></em>-Fe<em><sub>y</sub></em>@HhNS) were designed for step-by-step oxidative conversion of lignin into diethyl meleate (DEM). 92.0 % conversion of lignin with an exceptional DEM yield of 31.2 wt% and selectivity of 70.7 % was achieved at 150 °C for 24 h using Cu<sub>2.5</sub>-Fe<sub>2.2</sub>@HhNS. A series of controlled experiments and characterization showed clearly that the superior performance in DEM production was attributed to the enhanced tandem processes of lignin C<em><sub>α</sub></em>-C<em><sub>β</sub></em> bonds deconstruction by framework Cu<sup>2+</sup>, subsequently aromatic ring-cleavage by the isolated framework Fe<sup>3+</sup>, and the well-balanced micro-/mesoporosity ratio of Cu<em><sub>x</sub></em>-Fe<em><sub>y</sub></em>@HhNS facilitates the diffusion of lignin macromolecules/products, contributing to the excellent DEM yield and selectivity as well. Further mechanistic investigation illustrated that the process proceeds <em>via</em> a single electron transfer pathway. Consequently, this work provides new insights into lignin valorization to bulk chemicals, paving the way for biomass-derived recyclable polymeric materials as sustainable alternative to traditional petroleum-based routes.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"10 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849888","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}
Trans-2-butene is regularly burned as a liquefied petroleum gas (LPG) component in several developing countries due to its inertness and inseparability in comparison to other butene isomers (1-butene and isobutene), resulting in low-value utilization of resource and environmental degradation. The generation of high-carbon olefins via trans-2-butene oligomerization has become one of the most effective ways for its high-value valorization. Octene is currently undersupplied via ethylene oligomerization, and its traditional crafts are costly due to separation from full-fraction α-olefins (C4-C30). In the present work, we synthesized a series of novel 2-phenyl-ketimine-1,10-phenanthroline iron complexes (Fe0-Fe9). Fe2 catalyst realizes the dimerization of trans-2-butene through homogeneous catalysis at moderate conditions (0.2 MPa, 30 °C), obtaining 3,4-dimethyl-1-hexene with 99.9 % selectivity. In contrast to the reported heterogeneous catalysts, our catalytic system exhibits a considerable improvement in activity and selectivity.
{"title":"Unparalleled dimerization of trans-2-butene to 3,4-dimethyl-1-hexene on iron-based catalyst","authors":"Kang Gao, Guangjing Feng, Chaoan Liang, Zhuang Wang, Xiaoyan Sun, Jianhua Liu, Chungu Xia, Yuxiao Ding","doi":"10.1016/j.jcat.2025.116155","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116155","url":null,"abstract":"<em>Trans</em>-2-butene is regularly burned as a liquefied petroleum gas (LPG) component in several developing countries due to its inertness and inseparability in comparison to other butene isomers (1-butene and isobutene), resulting in low-value utilization of resource and environmental degradation. The generation of high-carbon olefins via <em>trans</em>-2-butene oligomerization has become one of the most effective ways for its high-value valorization. Octene is currently undersupplied via ethylene oligomerization, and its traditional crafts are costly due to separation from full-fraction α-olefins (C<sub>4</sub>-C<sub>30</sub>). In the present work, we synthesized a series of novel 2-phenyl-ketimine-1,10-phenanthroline iron complexes (Fe0-Fe9). Fe2 catalyst realizes the dimerization of <em>trans</em>-2-butene through homogeneous catalysis at moderate conditions (0.2 MPa, 30 °C), obtaining 3,4-dimethyl-1-hexene with 99.9 % selectivity. In contrast to the reported heterogeneous catalysts, our catalytic system exhibits a considerable improvement in activity and selectivity.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"135 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849887","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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