Pub Date : 2026-02-02DOI: 10.1021/acscatal.5c07653
Deep M. Patel,Nawaf M. Alghamdi,Christos M. Kalamaras,Zainab Al-Saihati,Dionisios G. Vlachos
Hydrogen internal combustion engines necessitate the implementation of selective catalytic reduction of nitrogen oxides under O2-rich environments in exhaust. This is challenging as noble metals favor combustion, selectively burning H2 instead of reducing NO to N2. Yet, high NO conversion and selectivity to N2 can be achieved on Pt/Al2O3 catalysts at low temperatures. To rationalize this paradox, we construct a microkinetic model on Pt(111) using electronic-structure calculations and find that the model fails to capture experiments. We conjecture that high-performing reduction catalysts consist of small metal clusters. Density functional theory calculations on Pt dimers supported on γ-Al2O3(110) (Pt2/Al2O3) reveal lower activation energies for NO dissociation and N–N recombination than O2 dissociation and N–NO recombination, respectively. Electron density difference isosurfaces suggest that lower-lying and partially occupied π* orbitals of NO require significantly less electron back-donation from Pt2 for bond activation than those of O2, rationalizing the lower NO dissociation barrier compared to O2. The higher barrier of N–NO recombination is likely due to the NO binding in a stable Oδ−–Nδ+ state. State-based microkinetic model accurately describes experimental observations and reveals a spatially varying Pt oxidized state, where NO reduction occurs on metallic states. Interestingly, the oxidation–reduction selectivity reverses at the extremes of metal size.
{"title":"Reaction Pathways in H2–Assisted NO Reduction on Alumina-Supported Platinum Clusters and Extended Surfaces","authors":"Deep M. Patel,Nawaf M. Alghamdi,Christos M. Kalamaras,Zainab Al-Saihati,Dionisios G. Vlachos","doi":"10.1021/acscatal.5c07653","DOIUrl":"https://doi.org/10.1021/acscatal.5c07653","url":null,"abstract":"Hydrogen internal combustion engines necessitate the implementation of selective catalytic reduction of nitrogen oxides under O2-rich environments in exhaust. This is challenging as noble metals favor combustion, selectively burning H2 instead of reducing NO to N2. Yet, high NO conversion and selectivity to N2 can be achieved on Pt/Al2O3 catalysts at low temperatures. To rationalize this paradox, we construct a microkinetic model on Pt(111) using electronic-structure calculations and find that the model fails to capture experiments. We conjecture that high-performing reduction catalysts consist of small metal clusters. Density functional theory calculations on Pt dimers supported on γ-Al2O3(110) (Pt2/Al2O3) reveal lower activation energies for NO dissociation and N–N recombination than O2 dissociation and N–NO recombination, respectively. Electron density difference isosurfaces suggest that lower-lying and partially occupied π* orbitals of NO require significantly less electron back-donation from Pt2 for bond activation than those of O2, rationalizing the lower NO dissociation barrier compared to O2. The higher barrier of N–NO recombination is likely due to the NO binding in a stable Oδ−–Nδ+ state. State-based microkinetic model accurately describes experimental observations and reveals a spatially varying Pt oxidized state, where NO reduction occurs on metallic states. Interestingly, the oxidation–reduction selectivity reverses at the extremes of metal size.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"79 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097936","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}
2,6-Naphthalenedicarboxylic acid (2,6-NDA) is a key monomer for high-performance poly(ethylene naphthalate) (PEN), which is currently produced industrially from petroleum resources via a complex six-step process. Here, a renewable route for the synthesis of 2,6-NDA with an overall yield of 86% from biobased building blocks p-toluquinone and isoprene was developed through a three-step cascade process: (1) a zinc-containing ionic liquid-catalyzed Diels–Alder cycloaddition of methyl-p-benzoquinone and isoprene to construct the dicyclic precursor 2,6-dimethyl-4a,5,8,8a-tetrahydro-[1,4]naphthoquinone (ProDA), (2) a Cu/SiO2-catalyzed dehydroaromatization-hydrodeoxygenation (DHA-HDO) of ProDA to 2,6-dimethylnaphthalene, and (3) oxidation of 2,6-dimethylnaphthalene using the commercial Co–Mn–Br catalytic system to afford 2,6-naphthalenedicarboxylic acid. In the critical and challenging DHA-HDO step, a copper-phyllosilicate-derived Cu/SiO2 catalyst with adsorption-promotion of Cu0 sites by adjacent Cu+ species plays a key role in the efficient adsorption and transformation of ProDA. This strategy is readily applicable to the synthesis of diverse (multi)methylated naphthalenes, providing a petroleum-independent solution for producing valuable bicyclic aromatic compounds.
{"title":"Production of 2,6-Naphthalenedicarboxylic Acid from Biomass-Derived Platform Compounds","authors":"Qingwei Meng, Yuxue Xiao, Chengwu Qiu, Xiaoli Pan, Changzhi Li, Xingwu Liu, Tao Zhang","doi":"10.1021/acscatal.5c07360","DOIUrl":"https://doi.org/10.1021/acscatal.5c07360","url":null,"abstract":"2,6-Naphthalenedicarboxylic acid (2,6-NDA) is a key monomer for high-performance poly(ethylene naphthalate) (PEN), which is currently produced industrially from petroleum resources via a complex six-step process. Here, a renewable route for the synthesis of 2,6-NDA with an overall yield of 86% from biobased building blocks <i>p</i>-toluquinone and isoprene was developed through a three-step cascade process: (1) a zinc-containing ionic liquid-catalyzed Diels–Alder cycloaddition of <i>methyl-p-benzoquinone</i> and isoprene to construct the dicyclic precursor 2,6-dimethyl-4a,5,8,8a-tetrahydro-[1,4]naphthoquinone (Pro<sub>DA</sub>), (2) a Cu/SiO<sub>2</sub>-catalyzed dehydroaromatization-hydrodeoxygenation (DHA-HDO) of Pro<sub>DA</sub> to 2,6-dimethylnaphthalene, and (3) oxidation of 2,6-dimethylnaphthalene using the commercial Co–Mn–Br catalytic system to afford 2,6-naphthalenedicarboxylic acid. In the critical and challenging DHA-HDO step, a copper-phyllosilicate-derived Cu/SiO<sub>2</sub> catalyst with adsorption-promotion of Cu<sup>0</sup> sites by adjacent Cu<sup>+</sup> species plays a key role in the efficient adsorption and transformation of Pro<sub>DA</sub>. This strategy is readily applicable to the synthesis of diverse (multi)methylated naphthalenes, providing a petroleum-independent solution for producing valuable bicyclic aromatic compounds.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"31 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098121","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 : 2026-02-01DOI: 10.1021/acscatal.5c08798
Yanpu Niu, Haolan Tao, Honglai Liu, Jingkun Li, Cheng Lian
The electrocatalytic CO2 reduction reaction (CO2RR) is a technology to utilize fluctuating renewable energy and close the carbon cycle. Cations play a vital role in interfacial reaction behaviors, which further affect the activity and selectivity of CO2RR. Current insights mainly focus on analyzing cation effects on the reaction kinetics of key intermediates, but a systematic understanding of cation effects cannot ignore the role of adsorption–desorption behaviors in the overall CO2RR performance. In this work, we highlight the effects of K+ on the adsorption and desorption dynamics of both CO2 and CO molecules through ab initio molecular dynamics simulations. We find K+ promotes CO2 adsorption and inhibits *CO desorption dynamically, thereby breaking the dynamic adsorption–desorption equilibrium, which benefits the *CO2 protonation and *CO–CO coupling. The enhanced chemisorption contribution of CO2/CO, arising from the cation-modulated hybridization of molecular orbitals, accounts for the regulation effect on the CO2/CO adsorption–desorption equilibrium. Furthermore, the cation-induced chemisorption of C1 molecules is a widespread phenomenon over various catalysts, including Cu(100), Cu(211), Au(110), Cu/Au(100) single-atom alloy, and Cu–N–C single-atom catalyst. Our study offers another insight into the cation effect on the CO2RR and highlights the significance of cations for interfacial transport of molecules.
{"title":"Cation Regulates Adsorption–Desorption Behaviors To Promote Electrochemical CO2 Reduction Reaction","authors":"Yanpu Niu, Haolan Tao, Honglai Liu, Jingkun Li, Cheng Lian","doi":"10.1021/acscatal.5c08798","DOIUrl":"https://doi.org/10.1021/acscatal.5c08798","url":null,"abstract":"The electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) is a technology to utilize fluctuating renewable energy and close the carbon cycle. Cations play a vital role in interfacial reaction behaviors, which further affect the activity and selectivity of CO<sub>2</sub>RR. Current insights mainly focus on analyzing cation effects on the reaction kinetics of key intermediates, but a systematic understanding of cation effects cannot ignore the role of adsorption–desorption behaviors in the overall CO<sub>2</sub>RR performance. In this work, we highlight the effects of K<sup>+</sup> on the adsorption and desorption dynamics of both CO<sub>2</sub> and CO molecules through ab initio molecular dynamics simulations. We find K<sup>+</sup> promotes CO<sub>2</sub> adsorption and inhibits *CO desorption dynamically, thereby breaking the dynamic adsorption–desorption equilibrium, which benefits the *CO<sub>2</sub> protonation and *CO–CO coupling. The enhanced chemisorption contribution of CO<sub>2</sub>/CO, arising from the cation-modulated hybridization of molecular orbitals, accounts for the regulation effect on the CO<sub>2</sub>/CO adsorption–desorption equilibrium. Furthermore, the cation-induced chemisorption of C1 molecules is a widespread phenomenon over various catalysts, including Cu(100), Cu(211), Au(110), Cu/Au(100) single-atom alloy, and Cu–N–C single-atom catalyst. Our study offers another insight into the cation effect on the CO<sub>2</sub>RR and highlights the significance of cations for interfacial transport of molecules.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"13 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098157","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 C═O selective hydrogenation of furfural (FAL) is challenging due to the competitive adsorption of C═C and C═O. Herein, Pt nanoclusters with different average valences are synthesized by the deposition precipitation strategy. Notably, the FAL hydrogenation activity shows a volcano trend with increasing Pt average valence. Importantly, the Pt nanocluster catalyst with an average valence of +0.97 (Pt cluster-300) exhibits a 99.6% FAL conversion and 100.0% furfuryl alcohol (FOL) selectivity during furfural hydrogenation, close to the world record level. UV–visible spectroscopy studies indicate that Pt cluster-300 exhibits the highest adsorption capacity for FAL compared to other catalysts in this study. Further theoretical calculations reveal the high catalytic activity of Pt cluster-300 mainly derives from the higher hybridization between the d orbital of Pt and the 2p orbital of C═O bond in FAL molecules, indicating the moderate Pt valence exhibits better ability to activate the C═O bond in FAL and thus enhancing the hydrogenation kinetics. This work provides insight into the influence mechanism of metal valence during hydrogenation reactions.
{"title":"Oxidation State of Highly Dispersed Pt Subnanoclusters Correlates with d–p Orbital Hybridization for 100% Selectivity in Furfural Hydrogenation","authors":"Xin Li, Jianguo Wu, Xuning Wang, Cuiwei Xu, Shoufan Hu, Dong Cao, Daojian Cheng","doi":"10.1021/acscatal.5c07387","DOIUrl":"https://doi.org/10.1021/acscatal.5c07387","url":null,"abstract":"The C═O selective hydrogenation of furfural (FAL) is challenging due to the competitive adsorption of C═C and C═O. Herein, Pt nanoclusters with different average valences are synthesized by the deposition precipitation strategy. Notably, the FAL hydrogenation activity shows a volcano trend with increasing Pt average valence. Importantly, the Pt nanocluster catalyst with an average valence of +0.97 (Pt cluster-300) exhibits a 99.6% FAL conversion and 100.0% furfuryl alcohol (FOL) selectivity during furfural hydrogenation, close to the world record level. UV–visible spectroscopy studies indicate that Pt cluster-300 exhibits the highest adsorption capacity for FAL compared to other catalysts in this study. Further theoretical calculations reveal the high catalytic activity of Pt cluster-300 mainly derives from the higher hybridization between the d orbital of Pt and the 2p orbital of C═O bond in FAL molecules, indicating the moderate Pt valence exhibits better ability to activate the C═O bond in FAL and thus enhancing the hydrogenation kinetics. This work provides insight into the influence mechanism of metal valence during hydrogenation reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"80 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098123","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 : 2026-01-31DOI: 10.1021/acscatal.5c07032
Yoshiki Hasukawa, Fernando Garcia-Escobar, Shun Nishimura, Lauren Takahashi, Keisuke Takahashi
Design of CO2 methanation catalysts is carried out by using literature data and machine learning. Key descriptors governing catalytic performance are identified via feature engineering, enabling accurate prediction of active bimetallic catalyst compositions. The predicted catalyst (NiSm/Al2O3) is synthesized and evaluated in a gas-flow heterogeneous reactor, where it achieves high CO2 conversion. Structural and surface properties are also investigated to characterize it. The performed approach demonstrates that descriptor design provides a powerful strategy for the discovery and rational development of heterogeneous catalysts.
{"title":"Descriptor Identification and Synthesis of Bimetallic Catalysts for CO2 Methanation","authors":"Yoshiki Hasukawa, Fernando Garcia-Escobar, Shun Nishimura, Lauren Takahashi, Keisuke Takahashi","doi":"10.1021/acscatal.5c07032","DOIUrl":"https://doi.org/10.1021/acscatal.5c07032","url":null,"abstract":"Design of CO<sub>2</sub> methanation catalysts is carried out by using literature data and machine learning. Key descriptors governing catalytic performance are identified via feature engineering, enabling accurate prediction of active bimetallic catalyst compositions. The predicted catalyst (NiSm/Al<sub>2</sub>O<sub>3</sub>) is synthesized and evaluated in a gas-flow heterogeneous reactor, where it achieves high CO<sub>2</sub> conversion. Structural and surface properties are also investigated to characterize it. The performed approach demonstrates that descriptor design provides a powerful strategy for the discovery and rational development of heterogeneous catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"56 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089688","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 : 2026-01-31DOI: 10.1021/acscatal.5c08237
Zhen Song, Chen He, Xinmiao Huang, Qian Ni, Yuan Hu, Ming Ma, Xuefeng Cong, Yuanhong Ma
The catalytic propargyl–silyl reductive coupling of propargyl electrophiles with silyl electrophiles represents an efficient approach to accessing propargylsilanes, which are versatile building blocks in synthetic and pharmaceutical chemistry. However, such a catalytic transformation has remained elusive and highly challenging. Herein, we report a regioselective cross-electrophile propargyl–silyl coupling of propargyl chlorides or esters with hydrochlorosilanes by chromium catalysis under mild conditions, providing an efficient and straightforward route for the synthesis of diverse propargyl hydrosilanes with broad substrate scope, good functional group compatibility, and high propargylic selectivity. Mechanistic studies suggest that the coupling reaction proceeds through a Cr(III)/Cr(II) cycle involving the generation of a propargyl radical via a single-electron transfer process, followed by the radical capture by a Cr(II) species to form a propargyl-Cr(III) species, and subsequent reduction by Mn and substitution with the Si–Cl bond in hydrochlorosilanes by the resulting propargyl-Cr(II) species.
{"title":"Regioselective Cross-Electrophile Propargyl–Silyl Coupling with Hydrochlorosilanes by Chromium Catalysis","authors":"Zhen Song, Chen He, Xinmiao Huang, Qian Ni, Yuan Hu, Ming Ma, Xuefeng Cong, Yuanhong Ma","doi":"10.1021/acscatal.5c08237","DOIUrl":"https://doi.org/10.1021/acscatal.5c08237","url":null,"abstract":"The catalytic propargyl–silyl reductive coupling of propargyl electrophiles with silyl electrophiles represents an efficient approach to accessing propargylsilanes, which are versatile building blocks in synthetic and pharmaceutical chemistry. However, such a catalytic transformation has remained elusive and highly challenging. Herein, we report a regioselective cross-electrophile propargyl–silyl coupling of propargyl chlorides or esters with hydrochlorosilanes by chromium catalysis under mild conditions, providing an efficient and straightforward route for the synthesis of diverse propargyl hydrosilanes with broad substrate scope, good functional group compatibility, and high propargylic selectivity. Mechanistic studies suggest that the coupling reaction proceeds through a Cr(III)/Cr(II) cycle involving the generation of a propargyl radical via a single-electron transfer process, followed by the radical capture by a Cr(II) species to form a propargyl-Cr(III) species, and subsequent reduction by Mn and substitution with the Si–Cl bond in hydrochlorosilanes by the resulting propargyl-Cr(II) species.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"23 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089689","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 : 2026-01-30DOI: 10.1021/acscatal.5c07909
Guimei Liu, Shiyuan Liu, Jie Wu, Tsz Shan Choy, Yan Sun, Gongjin Chen, Yan Zhang, Lanlu Lu, Yoonseob Kim, Wei Xing, Minhua Shao
Developing highly effective Ru-based electrocatalysts for the hydrogen oxidation reaction (HOR) is essential for driving the commercialization of anion exchange membrane fuel cells (AEMFCs) to address concerns regarding the performance and cost of anodic materials. In this study, well-dispersed vanadium oxide species (VOx) decorated on Ru particles were fabricated and used as an anode in AEMFC. This catalyst exhibited high HOR activity and durability, achieving a 1.2 W cm–2 peak power density under H2–O2, surpassing the performance of commercial Pt/C with identical metal loading (0.1 mg cm–2) under the same operating conditions. Experimental and calculation results indicate that the introduced VOx species modulate the electronic structures of Ru, optimizing hydrogen and hydroxyl binding energies and improving the electrochemical stability of Ru. This work opens opportunities for the rational design of catalysts via dispersing the oxophilic sites.
开发用于氢氧化反应（HOR）的高效钌基电催化剂对于推动阴离子交换膜燃料电池（aemfc）的商业化至关重要，以解决阳极材料的性能和成本问题。在这项研究中，制备了分散良好的氧化钒（VOx），并将其装饰在Ru颗粒上作为AEMFC的阳极。该催化剂具有较高的HOR活性和耐久性，在H2-O2条件下达到1.2 W cm-2的峰值功率密度，超过了在相同操作条件下具有相同金属负载（0.1 mg cm-2）的商用Pt/C的性能。实验和计算结果表明，引入的VOx物质可以调节Ru的电子结构，优化氢和羟基的结合能，提高Ru的电化学稳定性。这项工作为通过分散亲氧位点来合理设计催化剂提供了机会。
{"title":"Enhancing Hydrogen Oxidation Reaction Activity of Ruthenium by Vanadium Oxides","authors":"Guimei Liu, Shiyuan Liu, Jie Wu, Tsz Shan Choy, Yan Sun, Gongjin Chen, Yan Zhang, Lanlu Lu, Yoonseob Kim, Wei Xing, Minhua Shao","doi":"10.1021/acscatal.5c07909","DOIUrl":"https://doi.org/10.1021/acscatal.5c07909","url":null,"abstract":"Developing highly effective Ru-based electrocatalysts for the hydrogen oxidation reaction (HOR) is essential for driving the commercialization of anion exchange membrane fuel cells (AEMFCs) to address concerns regarding the performance and cost of anodic materials. In this study, well-dispersed vanadium oxide species (VO<sub><i>x</i></sub>) decorated on Ru particles were fabricated and used as an anode in AEMFC. This catalyst exhibited high HOR activity and durability, achieving a 1.2 W cm<sup>–2</sup> peak power density under H<sub>2</sub>–O<sub>2</sub>, surpassing the performance of commercial Pt/C with identical metal loading (0.1 mg cm<sup>–2</sup>) under the same operating conditions. Experimental and calculation results indicate that the introduced VO<sub><i>x</i></sub> species modulate the electronic structures of Ru, optimizing hydrogen and hydroxyl binding energies and improving the electrochemical stability of Ru. This work opens opportunities for the rational design of catalysts via dispersing the oxophilic sites.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"80 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089692","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 : 2026-01-30DOI: 10.1021/acscatal.5c07737
Wenjie Liu, Huibo Zhao, Xianyue Wu, Jianfeng Wu, Lingjun Chou, George Dury, Wenting Hu, Mikhail V. Polynski, Arravind Subramanian, Sergey M. Kozlov, Wen Liu
Understanding factors controlling product selectivity in CO2 hydrogenation remains a central research theme for catalytic CO2 utilization. Here, we report a composition-dependent selectivity anomaly in the In–Pd intermetallic series (viz., InPd2, InPd, In3Pd2), where In3Pd2 exhibits 100% CO selectivity via the reverse water–gas shift (RWGS) pathway, in sharp contrast to the high methanol selectivity achieved on other In-rich or Pd-rich metals or intermetallic compounds. Comprehensive characterization reveals that this anomaly arises from Pd enrichment on the surface of In3Pd2 IMC nanoparticles. The enriched Pd sites, modulated by In-to-Pd electron transfer, favor CO formation. In addition, the In-rich sites neighboring the Pd-rich islands facilitate rapid CO desorption. The resulting nanostructure on the surface of In3Pd2 IMCs renders an electronic interaction between In and Pd to promote CO formation and suppress C–H bond formation. This rationale is supported by both density functional theory (DFT) calculations and experimental evidence. These findings demonstrate that compositional control in intermetallic catalysts enables switchable CO2 hydrogenation selectivity and offers a rational approach to designing catalysts with tailored product distributions.
{"title":"Selectivity Anomaly in CO2 Hydrogenation over In–Pd Intermetallic Compounds","authors":"Wenjie Liu, Huibo Zhao, Xianyue Wu, Jianfeng Wu, Lingjun Chou, George Dury, Wenting Hu, Mikhail V. Polynski, Arravind Subramanian, Sergey M. Kozlov, Wen Liu","doi":"10.1021/acscatal.5c07737","DOIUrl":"https://doi.org/10.1021/acscatal.5c07737","url":null,"abstract":"Understanding factors controlling product selectivity in CO<sub>2</sub> hydrogenation remains a central research theme for catalytic CO<sub>2</sub> utilization. Here, we report a composition-dependent selectivity anomaly in the In–Pd intermetallic series (viz., InPd<sub>2</sub>, InPd, In<sub>3</sub>Pd<sub>2</sub>), where In<sub>3</sub>Pd<sub>2</sub> exhibits 100% CO selectivity via the reverse water–gas shift (RWGS) pathway, in sharp contrast to the high methanol selectivity achieved on other In-rich or Pd-rich metals or intermetallic compounds. Comprehensive characterization reveals that this anomaly arises from Pd enrichment on the surface of In<sub>3</sub>Pd<sub>2</sub> IMC nanoparticles. The enriched Pd sites, modulated by In-to-Pd electron transfer, favor CO formation. In addition, the In-rich sites neighboring the Pd-rich islands facilitate rapid CO desorption. The resulting nanostructure on the surface of In<sub>3</sub>Pd<sub>2</sub> IMCs renders an electronic interaction between In and Pd to promote CO formation and suppress C–H bond formation. This rationale is supported by both density functional theory (DFT) calculations and experimental evidence. These findings demonstrate that compositional control in intermetallic catalysts enables switchable CO<sub>2</sub> hydrogenation selectivity and offers a rational approach to designing catalysts with tailored product distributions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"51 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098124","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}
Photocatalytic CO2 reduction into value-added fuels has garnered considerable attention as a strategy to mitigate global warming and fossil fuel depletion. However, under practical aerobic conditions, photocatalytic activity often declines dramatically due to undesirable O2-photoreduction. Here, we show that deep eutectic solvents (DESs) can provide a protective reaction field against O2 while maintaining robust CO2 reduction performance using a Ru(II)-complex/Ag/polymeric carbon nitride (PCN) ternary hybrid photocatalyst. The turnover number of formic acid reached 1300 with 96% selectivity, and the apparent quantum yield was 2.7% in ethaline, composed of choline chloride and ethylene glycol, under pure CO2 conditions. Notably, ethaline retained 84% of its formic acid productivity under aerobic conditions with high selectivity, whereas the same catalyst showed only 63%, 42%, 28%, and 4% productivity in DMSO, DMA, MeOH, and MeCN, respectively. The protective nature of ethaline against O2 was also found in another hybrid photocatalyst consisting of a binuclear Ru(II) complex and Ag/PCN. This superior protective reaction field against O2 stems primarily from the low oxygen solubility and the low oxygen diffusion coefficient of ethaline. At the same time, its high CO2 solubility, biodegradability, and nonvolatility make it a promising solvent for CO2 reduction in O2-containing environments─an important step toward practical photocatalytic applications.
{"title":"Protective Reaction Fields Created by Deep Eutectic Solvents against Molecular Oxygen in CO2 Reduction over Ru(II)-Complex/Ag/Polymeric Carbon Nitride Hybrid Photocatalysts","authors":"Jo Onodera, Xian Zhang, Toshiya Tanaka, Ryuichi Nakada, Megumi Okazaki, Naoki Tarutani, Kiyofumi Katagiri, Kazuhiko Maeda","doi":"10.1021/acscatal.5c07569","DOIUrl":"https://doi.org/10.1021/acscatal.5c07569","url":null,"abstract":"Photocatalytic CO<sub>2</sub> reduction into value-added fuels has garnered considerable attention as a strategy to mitigate global warming and fossil fuel depletion. However, under practical aerobic conditions, photocatalytic activity often declines dramatically due to undesirable O<sub>2</sub>-photoreduction. Here, we show that deep eutectic solvents (DESs) can provide a protective reaction field against O<sub>2</sub> while maintaining robust CO<sub>2</sub> reduction performance using a Ru(II)-complex/Ag/polymeric carbon nitride (PCN) ternary hybrid photocatalyst. The turnover number of formic acid reached 1300 with 96% selectivity, and the apparent quantum yield was 2.7% in ethaline, composed of choline chloride and ethylene glycol, under pure CO<sub>2</sub> conditions. Notably, ethaline retained 84% of its formic acid productivity under aerobic conditions with high selectivity, whereas the same catalyst showed only 63%, 42%, 28%, and 4% productivity in DMSO, DMA, MeOH, and MeCN, respectively. The protective nature of ethaline against O<sub>2</sub> was also found in another hybrid photocatalyst consisting of a binuclear Ru(II) complex and Ag/PCN. This superior protective reaction field against O<sub>2</sub> stems primarily from the low oxygen solubility and the low oxygen diffusion coefficient of ethaline. At the same time, its high CO<sub>2</sub> solubility, biodegradability, and nonvolatility make it a promising solvent for CO<sub>2</sub> reduction in O<sub>2</sub>-containing environments─an important step toward practical photocatalytic applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"210 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089772","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}
Enhancing interfacial hydrogen bond (HB) network connectivity has been demonstrated as an effective strategy to accelerate 5-hydroxymethylfurfural electrooxidation by facilitating proton transfer. However, conventional HB networks lack structural flexibility, which severely restricts the mass diffusion of HMF and the products, thereby compromising the overall reaction rate. To overcome this limitation, a dynamically responsive HB network is constructed via self-adaptive W doping into nickel–iron hydroxide (W-NiFe), which not only ensures smooth reactant/product transport but also enables bidirectional modulation of external proton and internal electron transfer. On the protonic side, hydroxyl is selectively adsorbed and coordinates with interfacial K+ to directionally recruit free water molecules, thereby reinforcing HB network connectivity. This intelligently engineered network dynamically serves as a rapid proton-relay pathway, promptly dispersing the accumulated protons, mitigating localized acidification, and stabilizing the high-valence Ni sites. Concurrently, on the electronic side, W drives the fast generation of active high-valence Ni species by enabling a directed and swift electron transfer from Ni to W. Benefiting from this synergistic modulation, the optimized W-NiFe requires a low potential of 1.36 V to achieve 10 mA cm–2 and yields 2,5-furandicarboxylic acid with a high Faradaic efficiency of 95.49%. Moreover, thanks to the suppressed acid corrosion, W-NiFe can stably operate for ∼300 h at a high current density of 500 mA cm–2. This work provides fundamental insight into the design of adaptive interfacial structures for advanced electrocatalytic biomass refining.
增强界面氢键（HB）网络连通性已被证明是通过促进质子转移来加速5-羟甲基糠醛电氧化的有效策略。然而，传统的HB网络缺乏结构灵活性，这严重限制了HMF及其产物的质量扩散，从而影响了整体反应速率。为了克服这一限制，通过自适应W掺杂到氢氧化镍铁（W- nife）中构建了动态响应的HB网络，不仅保证了反应物/生成物的顺利传输，而且实现了外部质子和内部电子转移的双向调制。在质子侧，羟基被选择性吸附，并与界面K+配位，定向招募游离水分子，从而增强HB网络的连通性。这个智能设计的网络动态地作为一个快速的质子接力途径，迅速分散积累的质子，减轻局部酸化，并稳定高价Ni位点。同时，在电子方面，W通过从Ni到W的定向和快速电子转移来驱动活性高价Ni物质的快速生成。得益于这种协同调制，优化后的W- nife仅需1.36 V的低电位即可达到10 mA cm-2，并以95.49%的高法拉第效率生成2,5-呋喃二羧酸。此外，由于抑制了酸腐蚀，W-NiFe可以在500 mA cm-2的高电流密度下稳定工作~ 300小时。这项工作为先进的电催化生物质精炼的自适应界面结构的设计提供了基本的见解。
{"title":"Bidirectional Protonic-Electronic Modulation Based on Self-Adaptive Hydrogen Bond Network for 5-Hydroxymethylfurfural Oxidation","authors":"Feng-Ting Li, Sheng-Xia Yang, Hai-Jun Liu, Bin Dong, Yong-Ming Chai, Qun-Wei Tang, Xin-Yu Zhang, Ya-Nan Zhou","doi":"10.1021/acscatal.5c08159","DOIUrl":"https://doi.org/10.1021/acscatal.5c08159","url":null,"abstract":"Enhancing interfacial hydrogen bond (HB) network connectivity has been demonstrated as an effective strategy to accelerate 5-hydroxymethylfurfural electrooxidation by facilitating proton transfer. However, conventional HB networks lack structural flexibility, which severely restricts the mass diffusion of HMF and the products, thereby compromising the overall reaction rate. To overcome this limitation, a dynamically responsive HB network is constructed via self-adaptive W doping into nickel–iron hydroxide (W-NiFe), which not only ensures smooth reactant/product transport but also enables bidirectional modulation of external proton and internal electron transfer. On the protonic side, hydroxyl is selectively adsorbed and coordinates with interfacial K<sup>+</sup> to directionally recruit free water molecules, thereby reinforcing HB network connectivity. This intelligently engineered network dynamically serves as a rapid proton-relay pathway, promptly dispersing the accumulated protons, mitigating localized acidification, and stabilizing the high-valence Ni sites. Concurrently, on the electronic side, W drives the fast generation of active high-valence Ni species by enabling a directed and swift electron transfer from Ni to W. Benefiting from this synergistic modulation, the optimized W-NiFe requires a low potential of 1.36 V to achieve 10 mA cm<sup>–2</sup> and yields 2,5-furandicarboxylic acid with a high Faradaic efficiency of 95.49%. Moreover, thanks to the suppressed acid corrosion, W-NiFe can stably operate for ∼300 h at a high current density of 500 mA cm<sup>–2</sup>. This work provides fundamental insight into the design of adaptive interfacial structures for advanced electrocatalytic biomass refining.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"145 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097937","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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