Metal–organic frameworks (MOFs) have attracted significant attention for photocatalytic CO2 reduction due to their tunable pore environments, abundant active sites, and diverse stacking modes. However, the effect of different interlayer stacking, particularly when multiple stacking modes coexist within the same structure, remains underexplored. Here, we report a Copper-Melamine Framework (Cu-Mel-MOF) in which AA-rotated and AA-serrated stacking structures coexist in localized region: the 60° interlayer twist in the AA-rotated stacking induces the formation of a short-range Moiré superlattice, whereas the AA-serrated stacking exhibits staggered zigzag-like interlayer offsets. Under visible light irradiation, Cu-Mel-MOF achieves CO and H2 evolution rates of 6.27 and 3.96 mmol g–1 h–1, respectively, surpassing previously reported copper-based MOF photocatalysts. Grand Canonical Monte Carlo simulations reveal that among six stacking configurations, the serrated AA and AA-rotated stackings exhibit the highest CO2 and H2O adsorption capacities. Molecular dynamics simulations show that AA-rotated stacking reduces the CO2 activation energy (Ea = 0.20 eV), facilitating CO2 molecular transport. Density functional theory calculations further indicate that AA-rotated stacking possesses a higher CO2 adsorption energy (1.17 eV), while the serrated AA stacking exhibits a lower Gibbs free energy change in the *COOH adsorption step, enhancing overall photocatalytic performance. These findings highlight the pivotal role of stacking geometry in regulating the thermodynamics and kinetics of MOF-based photocatalysis, providing insights into molecular transport mechanisms and guiding the rational design of efficient MOF photocatalysts for CO2 conversion.
{"title":"Localized Coexistence of Moiré and Serrated Stackings in a Copper-Melamine Framework Boosts Photocatalytic CO2 Conversion","authors":"Xinhui Lu,Junhao Wu,Wei Zhou,Siqi Peng,Yuanyuan Zhu,Xiao Wang,Qianqian Yan,Jixia Qiu,Shuhua Yang,Sheng Zhang,Kui Li,Xing Lu","doi":"10.1021/acscatal.6c00568","DOIUrl":"https://doi.org/10.1021/acscatal.6c00568","url":null,"abstract":"Metal–organic frameworks (MOFs) have attracted significant attention for photocatalytic CO2 reduction due to their tunable pore environments, abundant active sites, and diverse stacking modes. However, the effect of different interlayer stacking, particularly when multiple stacking modes coexist within the same structure, remains underexplored. Here, we report a Copper-Melamine Framework (Cu-Mel-MOF) in which AA-rotated and AA-serrated stacking structures coexist in localized region: the 60° interlayer twist in the AA-rotated stacking induces the formation of a short-range Moiré superlattice, whereas the AA-serrated stacking exhibits staggered zigzag-like interlayer offsets. Under visible light irradiation, Cu-Mel-MOF achieves CO and H2 evolution rates of 6.27 and 3.96 mmol g–1 h–1, respectively, surpassing previously reported copper-based MOF photocatalysts. Grand Canonical Monte Carlo simulations reveal that among six stacking configurations, the serrated AA and AA-rotated stackings exhibit the highest CO2 and H2O adsorption capacities. Molecular dynamics simulations show that AA-rotated stacking reduces the CO2 activation energy (Ea = 0.20 eV), facilitating CO2 molecular transport. Density functional theory calculations further indicate that AA-rotated stacking possesses a higher CO2 adsorption energy (1.17 eV), while the serrated AA stacking exhibits a lower Gibbs free energy change in the *COOH adsorption step, enhancing overall photocatalytic performance. These findings highlight the pivotal role of stacking geometry in regulating the thermodynamics and kinetics of MOF-based photocatalysis, providing insights into molecular transport mechanisms and guiding the rational design of efficient MOF photocatalysts for CO2 conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"31 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506445","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 : 2026-03-24DOI: 10.1021/acscatal.5c09092
Isaac O. Ogabiela,R. Morgan Whitfield III,Oleksiy V. Shvets,Mykhailo M. Kurmach,Nataliya Shcherban,Javed Khan,Peng Bai,Friederike C. Jentoft
Aldol reactions can follow the classical condensation path and produce an α,β-unsaturated carbonyl compound and water, but in some cases, aldol chemistry may be steered toward a fission pathway that gives an olefin and a carboxylic acid. This investigation examines how the strength of Bro̷nsted acid sites─both in homogeneous and heterogeneous catalysis─controls these two pathways and their kinetics. The cross-aldol reaction between benzaldehyde and 3-pentanone served as a test case. Batch reactions, conducted in toluene as solvent at a temperature of 140 °C under autogenous pressure, were analyzed by GC and in situ ATR-FTIR spectroscopy to determine product distributions and rate constants for condensation and fission pathways. A series of soluble acids, including a family of sulfonic acids, mostly favored the condensation pathway, with formic acid as the weakest in the series, due to its pKa being inactive for aldol chemistry. Significant amounts of fission products were rare except for higher concentrations of benzenesulfonic acid and the known selectivity of phosphoric acid. For the sulfonic acid family, the logarithm of the first-order condensation rate coefficients scaled only roughly with pKa (water) values, whereas a good correlation was obtained with calculated deprotonation Gibbs energies in toluene. A series of H-forms of isomorphously substituted beta zeolites, HESiBEA with E = Al, Ga, Fe, or B, favored the fission pathway. Site density and site strength were characterized by calorimetric measurements of the heats of adsorption of isopropylamine, which decreased in the order Al > Ga, Fe > B. The logarithm of the site-normalized first-order fission rate coefficients scaled roughly with the heat of adsorption and correlated linearly with reported deprotonation energies. In conclusion, acid strength mainly affects activity and can be seen as a prerequisite for either aldol condensation or fission chemistry, whereas additional, yet to be fully clarified, catalyst properties and reaction conditions are required to steer aldol chemistry toward fission selectivity.
{"title":"Effect of Strength of Soluble and Solid Acid Catalysts on Selectivity in Aldol Reactions","authors":"Isaac O. Ogabiela,R. Morgan Whitfield III,Oleksiy V. Shvets,Mykhailo M. Kurmach,Nataliya Shcherban,Javed Khan,Peng Bai,Friederike C. Jentoft","doi":"10.1021/acscatal.5c09092","DOIUrl":"https://doi.org/10.1021/acscatal.5c09092","url":null,"abstract":"Aldol reactions can follow the classical condensation path and produce an α,β-unsaturated carbonyl compound and water, but in some cases, aldol chemistry may be steered toward a fission pathway that gives an olefin and a carboxylic acid. This investigation examines how the strength of Bro̷nsted acid sites─both in homogeneous and heterogeneous catalysis─controls these two pathways and their kinetics. The cross-aldol reaction between benzaldehyde and 3-pentanone served as a test case. Batch reactions, conducted in toluene as solvent at a temperature of 140 °C under autogenous pressure, were analyzed by GC and in situ ATR-FTIR spectroscopy to determine product distributions and rate constants for condensation and fission pathways. A series of soluble acids, including a family of sulfonic acids, mostly favored the condensation pathway, with formic acid as the weakest in the series, due to its pKa being inactive for aldol chemistry. Significant amounts of fission products were rare except for higher concentrations of benzenesulfonic acid and the known selectivity of phosphoric acid. For the sulfonic acid family, the logarithm of the first-order condensation rate coefficients scaled only roughly with pKa (water) values, whereas a good correlation was obtained with calculated deprotonation Gibbs energies in toluene. A series of H-forms of isomorphously substituted beta zeolites, HESiBEA with E = Al, Ga, Fe, or B, favored the fission pathway. Site density and site strength were characterized by calorimetric measurements of the heats of adsorption of isopropylamine, which decreased in the order Al > Ga, Fe > B. The logarithm of the site-normalized first-order fission rate coefficients scaled roughly with the heat of adsorption and correlated linearly with reported deprotonation energies. In conclusion, acid strength mainly affects activity and can be seen as a prerequisite for either aldol condensation or fission chemistry, whereas additional, yet to be fully clarified, catalyst properties and reaction conditions are required to steer aldol chemistry toward fission selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506446","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 : 2026-03-24DOI: 10.1021/acscatal.5c08361
Pengfei Hou,Jingshan Luo,Jin-Cheng Liu
Theoretical exploration of complex catalytic reaction networks (CRNs) is limited by the trade-off between the cost of quantum mechanical calculations and the reduced accuracy of approximate methods. We introduce the LFT-CRN, an active learning framework combining pretrained universal machine learning interatomic potentials (MLIPs) with a local fine-tuning (LFT) algorithm for efficient CRN exploration. The LFT-CRN accelerates geometry optimization, transition-state search, and vibrational analysis while maintaining consistent performance across different exchange–correlation functionals and density functional theory (DFT) settings. Applied to methanol synthesis on CuZn catalysts, the LFT-CRN achieves over a 14-fold acceleration compared with the conventional DFT workflow, retaining chemical accuracy (<1 kcal/mol) for several energy metrics. Energetics and microkinetic simulation reveal that low-coordination Cu sites with moderate Zn doping maximize both Cu–Zn synergy and catalytic activity, whereas excessive Zn reduces performance. This generalizable workflow enables high-throughput CRN exploration, thereby supporting catalyst design and optimization of industrial processes.
{"title":"Accelerating Catalytic Reaction Network Exploration via Local Fine-tuning with Universal Machine Learning Interatomic Potentials","authors":"Pengfei Hou,Jingshan Luo,Jin-Cheng Liu","doi":"10.1021/acscatal.5c08361","DOIUrl":"https://doi.org/10.1021/acscatal.5c08361","url":null,"abstract":"Theoretical exploration of complex catalytic reaction networks (CRNs) is limited by the trade-off between the cost of quantum mechanical calculations and the reduced accuracy of approximate methods. We introduce the LFT-CRN, an active learning framework combining pretrained universal machine learning interatomic potentials (MLIPs) with a local fine-tuning (LFT) algorithm for efficient CRN exploration. The LFT-CRN accelerates geometry optimization, transition-state search, and vibrational analysis while maintaining consistent performance across different exchange–correlation functionals and density functional theory (DFT) settings. Applied to methanol synthesis on CuZn catalysts, the LFT-CRN achieves over a 14-fold acceleration compared with the conventional DFT workflow, retaining chemical accuracy (<1 kcal/mol) for several energy metrics. Energetics and microkinetic simulation reveal that low-coordination Cu sites with moderate Zn doping maximize both Cu–Zn synergy and catalytic activity, whereas excessive Zn reduces performance. This generalizable workflow enables high-throughput CRN exploration, thereby supporting catalyst design and optimization of industrial processes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506448","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 : 2026-03-24DOI: 10.1021/acscatal.5c08499
Aleksandra Wawrzyniak,Mark Aarts,Marc T. M. Koper
In this study, we focus on improving the activity of electrochemical carbon monoxide (CO) reduction toward methanol (CH3OH) on a model catalyst reported previously by our group: a platinum(111) single crystal modified with a palladium monolayer (PdML/Pt(111)). Dynamic electrolysis with a square potential wave was applied at a negative potential of −0.8 V for CO, while the (more) positive potential was varied between −0.2 V and +0.8 V vs the Reversible Hydrogen Electrode (RHE) for different negative and positive pulse durations. We find a 7-fold increase (compared to static electrolysis) in Faradaic Efficiency (FE) for CO reduction toward methanol (12.6%) when the potential is pulsed between −0.8 and +0.4 V, with 1-s pulses, and an 11-fold increase when the potassium cation concentration in the electrolyte was raised to 1 M (20.1%). Additionally, a 5-fold improvement in the FECH3OH was found during dynamic carbon dioxide (CO2) electrolysis as well, when the potential is pulsed between −0.9 and +0.4 V. The surface of PdML/Pt(111) was investigated postcatalysis using cyclic voltammetry (CV), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). The formation of bilayer islands and the exposure of the Pt single-crystal surface were found using all three techniques. We find that applying dynamic electrolysis conditions significantly enhances methanol production under all probed conditions. This finding could be extended to other electrocatalysts facilitating methanol formation from CO(2) for improved performance and minimization of the Hydrogen Evolution Reaction.
{"title":"Dynamic CO Electrolysis to Methanol on Pt(111) Surfaces Modified with a Pd Monolayer","authors":"Aleksandra Wawrzyniak,Mark Aarts,Marc T. M. Koper","doi":"10.1021/acscatal.5c08499","DOIUrl":"https://doi.org/10.1021/acscatal.5c08499","url":null,"abstract":"In this study, we focus on improving the activity of electrochemical carbon monoxide (CO) reduction toward methanol (CH3OH) on a model catalyst reported previously by our group: a platinum(111) single crystal modified with a palladium monolayer (PdML/Pt(111)). Dynamic electrolysis with a square potential wave was applied at a negative potential of −0.8 V for CO, while the (more) positive potential was varied between −0.2 V and +0.8 V vs the Reversible Hydrogen Electrode (RHE) for different negative and positive pulse durations. We find a 7-fold increase (compared to static electrolysis) in Faradaic Efficiency (FE) for CO reduction toward methanol (12.6%) when the potential is pulsed between −0.8 and +0.4 V, with 1-s pulses, and an 11-fold increase when the potassium cation concentration in the electrolyte was raised to 1 M (20.1%). Additionally, a 5-fold improvement in the FECH3OH was found during dynamic carbon dioxide (CO2) electrolysis as well, when the potential is pulsed between −0.9 and +0.4 V. The surface of PdML/Pt(111) was investigated postcatalysis using cyclic voltammetry (CV), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). The formation of bilayer islands and the exposure of the Pt single-crystal surface were found using all three techniques. We find that applying dynamic electrolysis conditions significantly enhances methanol production under all probed conditions. This finding could be extended to other electrocatalysts facilitating methanol formation from CO(2) for improved performance and minimization of the Hydrogen Evolution Reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506447","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 : 2026-03-23DOI: 10.1021/acscatal.5c09200
Fan Chen,Jinming Wang,Yuan He,Dandan Liu,Lin Hu,Rui Shi,Yana Liu,Jiguang Zhang,Yunfeng Zhu,Jun Wang
Photocatalytic aerobic oxidation of methane (CH4) to methanol (CH3OH) offers an alternative to the current energy-intensive route for CH4 utilization, while suffering from the activity-selectivity trade-off due to the uncontrolled generation of reactive oxygen species (ROS). Herein, we perform the photocatalytic CH4 aerobic oxidation in the presence of H2 over a PdCu NPs-modified ZnO catalyst, which exhibits a CH3OH yield of 13.5 mmol gcat–1 h–1 and a selectivity of 71.1%, surpassing many previously reported results. The introduction of H2 enables more ROS production simultaneously from photoelectron-induced O2 reduction and in situ-produced H2O2, facilitating the conversion of CH4. Compared to Pd, the PdCu cocatalyst favors the generation of more •OOH radicals in the ROS. More importantly, it is proposed that intermediate CH3OOH can be converted to CH3OH by H2-derived Pd–H species, which could also scavenge the excessive •OH radicals and holes, thus promoting the productivity of CH3OH and suppressing overoxidation. This work provides a strategy to regulate ROS formation for efficient CH4 oxidation into CH3OH under mild conditions.
{"title":"Regulating Reactive Oxygen Species with H2 over PdCu/ZnO for Selective Photocatalytic Aerobic Oxidation of Methane to Methanol","authors":"Fan Chen,Jinming Wang,Yuan He,Dandan Liu,Lin Hu,Rui Shi,Yana Liu,Jiguang Zhang,Yunfeng Zhu,Jun Wang","doi":"10.1021/acscatal.5c09200","DOIUrl":"https://doi.org/10.1021/acscatal.5c09200","url":null,"abstract":"Photocatalytic aerobic oxidation of methane (CH4) to methanol (CH3OH) offers an alternative to the current energy-intensive route for CH4 utilization, while suffering from the activity-selectivity trade-off due to the uncontrolled generation of reactive oxygen species (ROS). Herein, we perform the photocatalytic CH4 aerobic oxidation in the presence of H2 over a PdCu NPs-modified ZnO catalyst, which exhibits a CH3OH yield of 13.5 mmol gcat–1 h–1 and a selectivity of 71.1%, surpassing many previously reported results. The introduction of H2 enables more ROS production simultaneously from photoelectron-induced O2 reduction and in situ-produced H2O2, facilitating the conversion of CH4. Compared to Pd, the PdCu cocatalyst favors the generation of more •OOH radicals in the ROS. More importantly, it is proposed that intermediate CH3OOH can be converted to CH3OH by H2-derived Pd–H species, which could also scavenge the excessive •OH radicals and holes, thus promoting the productivity of CH3OH and suppressing overoxidation. This work provides a strategy to regulate ROS formation for efficient CH4 oxidation into CH3OH under mild conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506455","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}
Highly dispersed Pt nanoclusters uniformly anchored on a mesoporous NbOPO4 were designed for efficient hydrodeoxygenation of fatty acids/methyl esters. This high activity stems from a P-induced electronic synergy: electron-deficient Nb5+ sites polarize carboxyl groups, while Ptδ+ clusters dissociate H2, with spillover hydrogen transported via P–OH bridges. This concerted mechanism drives direct dehydration-hydrogenation of a gem-diol/alkenol intermediate, bypassing aldehyde formation and suppressing decarboxylation. The catalyst demonstrates generality, affording near-theoretical yields of Cn alkanes from C12–C18 feedstocks (acids, esters, triglycerides) with a productivity of 415 gCn-alkane·gPt–1·h–1, rendering it highly competitive among those reported for sulfur-free hydroprocessed esters and fatty acid (HEFA) catalysts. The 0.1 wt % Pt/NbOPO4(0.3P) catalyst achieves quantitative, >99% yield conversion of palmitic acid to C16 alkanes under 3 MPa initial H2 pressure with required reaction times spanning from 4 to 12 h depending on feedstock complexity, significantly outperforming an impregnated 1 wt % Pt analog. DFT calculations confirm Nb5+ adsorption and polarization of the −COOH group and further demonstrate that the energy landscape is lower for Brønsted acid-mediated hydrogen spillover, which facilitates H migration to −COOH. This work elucidates the Brønsted acid and spillover effects that maximize noble-metal efficiency and establishes a scalable route for carbon-conservative HEFA.
{"title":"Ultralow-Loading Pt Clusters Synergizing with P–OH Sites for Efficient Hydrodeoxygenation of Fatty Acids/Methyl Esters","authors":"Wenjie Zhang,Jianguo Liu,Zhenquan Fang,Liangdong Hu,Yubao Chen,Yanfei Xu,Xinghua Zhang,Mingyue Ding,Longlong Ma,Lungang Chen","doi":"10.1021/acscatal.6c00217","DOIUrl":"https://doi.org/10.1021/acscatal.6c00217","url":null,"abstract":"Highly dispersed Pt nanoclusters uniformly anchored on a mesoporous NbOPO4 were designed for efficient hydrodeoxygenation of fatty acids/methyl esters. This high activity stems from a P-induced electronic synergy: electron-deficient Nb5+ sites polarize carboxyl groups, while Ptδ+ clusters dissociate H2, with spillover hydrogen transported via P–OH bridges. This concerted mechanism drives direct dehydration-hydrogenation of a gem-diol/alkenol intermediate, bypassing aldehyde formation and suppressing decarboxylation. The catalyst demonstrates generality, affording near-theoretical yields of Cn alkanes from C12–C18 feedstocks (acids, esters, triglycerides) with a productivity of 415 gCn-alkane·gPt–1·h–1, rendering it highly competitive among those reported for sulfur-free hydroprocessed esters and fatty acid (HEFA) catalysts. The 0.1 wt % Pt/NbOPO4(0.3P) catalyst achieves quantitative, >99% yield conversion of palmitic acid to C16 alkanes under 3 MPa initial H2 pressure with required reaction times spanning from 4 to 12 h depending on feedstock complexity, significantly outperforming an impregnated 1 wt % Pt analog. DFT calculations confirm Nb5+ adsorption and polarization of the −COOH group and further demonstrate that the energy landscape is lower for Brønsted acid-mediated hydrogen spillover, which facilitates H migration to −COOH. This work elucidates the Brønsted acid and spillover effects that maximize noble-metal efficiency and establishes a scalable route for carbon-conservative HEFA.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506453","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 : 2026-03-23DOI: 10.1021/acscatal.6c00816
Elizabeth J. Gross, Sophia G. Barthel, Carter U. Brzezinski, Logan Z. Hessefort, John Bacsa, Kyle F. Biegasiewicz
Organic chloramines are an important class of compounds containing a covalent nitrogen–chlorine bond. Despite the growing interest in their applications in small molecule synthesis and polymer science, selective catalyst systems for their preparation have remained elusive. We recently discovered that the vanadium-dependent chloroperoxidase from Curvularia inaequalis (CiVCPO) is an effective biocatalyst for selective chlorination of a broad range of structurally diverse amines to give the corresponding chloramines and chlorimines. The catalyst system is readily scalable and applied to chemoenzymatic nitrile and amide synthesis. Finally, halide divergent reactivity is demonstrated through chloride-selective chlorimine formation and bromide-selective aldehyde formation using the same biocatalyst.
{"title":"Chlorination of Amines by a Vanadium-Dependent Chloroperoxidase","authors":"Elizabeth J. Gross, Sophia G. Barthel, Carter U. Brzezinski, Logan Z. Hessefort, John Bacsa, Kyle F. Biegasiewicz","doi":"10.1021/acscatal.6c00816","DOIUrl":"https://doi.org/10.1021/acscatal.6c00816","url":null,"abstract":"Organic chloramines are an important class of compounds containing a covalent nitrogen–chlorine bond. Despite the growing interest in their applications in small molecule synthesis and polymer science, selective catalyst systems for their preparation have remained elusive. We recently discovered that the vanadium-dependent chloroperoxidase from <i>Curvularia inaequalis</i> (<i>Ci</i>VCPO) is an effective biocatalyst for selective chlorination of a broad range of structurally diverse amines to give the corresponding chloramines and chlorimines. The catalyst system is readily scalable and applied to chemoenzymatic nitrile and amide synthesis. Finally, halide divergent reactivity is demonstrated through chloride-selective chlorimine formation and bromide-selective aldehyde formation using the same biocatalyst.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495585","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}
Efficiently converting CO2 into high-yield light olefins via the CO2-modified Fischer–Tropsch synthesis (CO2–FTS) over iron-based catalysts remains a key challenge. Here, we report cobalt-promoted hydrogenation of CO2 to light olefins over Na–FeMn catalysts. Incorporation of cobalt enhances the CO2 conversion (59.6%) by accelerating CO formation via the reverse water–gas shift (RWGS) reaction, thereby increasing the availability of CO for subsequent FTS. Although cobalt increases the overall hydrogenation activity, the Na–FeMn framework maintains olefin formation pathways, leading to an improved light olefin yield of 22.33% with a selectivity of 39.6%. In situ X-ray diffraction (in situ XRD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) reveal the dynamic phase evolution of the catalyst and the transformation of surface intermediates under reaction conditions. The results indicate that cobalt primarily acts as a kinetic promoter that facilitates CO generation and intermediate turnover. This study clarifies the promotional role of cobalt in iron-based catalysts and provides insights into optimizing CO2 hydrogenation toward light olefins.
{"title":"High-Yield Production of Light Olefins from CO2 Hydrogenation over Co-Promoted Na–FeMn Catalysts","authors":"Ayaka Miura,Teng Li,Lijun Zhang,Jiaming Liang,Yitong Han,Hao Huang,Baojian Chen,Zhenkun Liu,Peng Qin,Kenji Nakao,Noriyuki Yamaneb,Caixia Zhu,Guangbo Liu,Prasert Reubroycharoen,Yingluo He,Zhiliang Jin,Mingbo Wu,Noritatsu Tsubaki","doi":"10.1021/acscatal.6c00962","DOIUrl":"https://doi.org/10.1021/acscatal.6c00962","url":null,"abstract":"Efficiently converting CO2 into high-yield light olefins via the CO2-modified Fischer–Tropsch synthesis (CO2–FTS) over iron-based catalysts remains a key challenge. Here, we report cobalt-promoted hydrogenation of CO2 to light olefins over Na–FeMn catalysts. Incorporation of cobalt enhances the CO2 conversion (59.6%) by accelerating CO formation via the reverse water–gas shift (RWGS) reaction, thereby increasing the availability of CO for subsequent FTS. Although cobalt increases the overall hydrogenation activity, the Na–FeMn framework maintains olefin formation pathways, leading to an improved light olefin yield of 22.33% with a selectivity of 39.6%. In situ X-ray diffraction (in situ XRD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) reveal the dynamic phase evolution of the catalyst and the transformation of surface intermediates under reaction conditions. The results indicate that cobalt primarily acts as a kinetic promoter that facilitates CO generation and intermediate turnover. This study clarifies the promotional role of cobalt in iron-based catalysts and provides insights into optimizing CO2 hydrogenation toward light olefins.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506449","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 : 2026-03-23DOI: 10.1021/acscatal.5c07991
Jingbin Huang, Chunhe Yu, Jie Zhu, Maoyuan Huang, Ziyu Zhang, Keke Zhang, Guanxin Zhang, Yuli Wang, Da Liu, Lin Jin, Renbing Wu
MoS2-based catalysts typically confront the critical challenge of balancing high catalytic activity and stability for the hydrogen evolution reaction (HER). This issue remains largely unresolved to date, seriously hindering their practical application. Herein, we develop a feasible molecule fence strategy to address this challenge by confining highly active Ni-doped MoS2 (Ni-MoS2) within a NiS2 fence featuring molecular selectivity. The combined density functional theory (DFT) calculations and in situ spectroscopy measurements reveal that the NiS2 layer as a molecule fence not only enhances the adsorption of H2O molecules but also protects Ni-MoS2 active components from the corrosion by O2 and OH– toxic species, thus greatly inhibiting the leaching of Ni-MoS2 as well as promoting its HER activity. Furthermore, the Ni-MoS2@NiS2-assembled anion exchange membrane water electrolysis (AEMWE) device can achieve a low voltage of 1.85 V to reach a current density of 1000 mA cm–2 and maintains a long-term operation for 1000 h. This study offers insights and valuable guidance for rational construction of electrocatalysts with high activity and stability.
基于二硫化钼的催化剂通常面临着平衡高催化活性和析氢反应（HER）稳定性的关键挑战。到目前为止，这个问题在很大程度上仍未解决，严重阻碍了它们的实际应用。在此，我们开发了一种可行的分子栅栏策略，通过将高活性的ni掺杂MoS2 （Ni-MoS2）限制在具有分子选择性的NiS2栅栏内来解决这一挑战。密度泛函理论（DFT）计算和原位光谱测量结果表明，NiS2层作为分子栅栏不仅增强了Ni-MoS2对H2O分子的吸附，而且保护Ni-MoS2活性组分不受O2和OH -有毒物质的腐蚀，从而大大抑制了Ni-MoS2的浸出，提高了Ni-MoS2的HER活性。此外，Ni-MoS2@NiS2-assembled阴离子交换膜电解（AEMWE）装置可以实现1.85 V的低电压，达到1000 mA cm-2的电流密度，并保持1000 h的长期运行。该研究为合理构建具有高活性和稳定性的电催化剂提供了见解和有价值的指导。
{"title":"Molecular Fence Strategy Disentangles the Activity–Stability Trade-Off for Alkaline Hydrogen Evolution","authors":"Jingbin Huang, Chunhe Yu, Jie Zhu, Maoyuan Huang, Ziyu Zhang, Keke Zhang, Guanxin Zhang, Yuli Wang, Da Liu, Lin Jin, Renbing Wu","doi":"10.1021/acscatal.5c07991","DOIUrl":"https://doi.org/10.1021/acscatal.5c07991","url":null,"abstract":"MoS<sub>2</sub>-based catalysts typically confront the critical challenge of balancing high catalytic activity and stability for the hydrogen evolution reaction (HER). This issue remains largely unresolved to date, seriously hindering their practical application. Herein, we develop a feasible molecule fence strategy to address this challenge by confining highly active Ni-doped MoS<sub>2</sub> (Ni-MoS<sub>2</sub>) within a NiS<sub>2</sub> fence featuring molecular selectivity. The combined density functional theory (DFT) calculations and in situ spectroscopy measurements reveal that the NiS<sub>2</sub> layer as a molecule fence not only enhances the adsorption of H<sub>2</sub>O molecules but also protects Ni-MoS<sub>2</sub> active components from the corrosion by O<sub>2</sub> and OH<sup>–</sup> toxic species, thus greatly inhibiting the leaching of Ni-MoS<sub>2</sub> as well as promoting its HER activity. Furthermore, the Ni-MoS<sub>2</sub>@NiS<sub>2</sub>-assembled anion exchange membrane water electrolysis (AEMWE) device can achieve a low voltage of 1.85 V to reach a current density of 1000 mA cm<sup>–2</sup> and maintains a long-term operation for 1000 h. This study offers insights and valuable guidance for rational construction of electrocatalysts with high activity and stability.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"146 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495584","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 : 2026-03-23DOI: 10.1021/acscatal.6c00690
Sikai Wang,Chang Liu,Xiaotong Jin,Yi Zhang,Jiwu Zhao,Wei Zhang,Xianhao Zhang,Rui Cao,Xialiang Li
The selective dioxygenation of indoles by heme enzymes is a significant biochemical process. Synthetic FeII porphyrins were used to catalyze indole dioxygenation, but the formation of μ-oxo-bridged FeIII–O–FeIII caused catalyst deactivation. Herein, we report a homogeneous electro-driven strategy to realize catalytic indole dioxygenation by Fe tetra(pentafluorophenyl)porphyrin with a turnover number up to 8825 and Faradaic efficiency exceeding 104%. In homogeneous catalysis, inert FeIII–O–FeIII, which is generated upon the oxidation of FeII porphyrin by FeIII-superoxo and/or FeIV═O, can be electrochemically reduced to FeII porphyrin to reinitiate catalysis. Moreover, we identified an intermediate formed between FeIII-superoxo and dimethylindole by in situ electrochemical mass spectrometry.
{"title":"Electro-driven Dioxygenation of Indole by Iron Porphyrin with Faradaic Efficiency Exceeding 104%","authors":"Sikai Wang,Chang Liu,Xiaotong Jin,Yi Zhang,Jiwu Zhao,Wei Zhang,Xianhao Zhang,Rui Cao,Xialiang Li","doi":"10.1021/acscatal.6c00690","DOIUrl":"https://doi.org/10.1021/acscatal.6c00690","url":null,"abstract":"The selective dioxygenation of indoles by heme enzymes is a significant biochemical process. Synthetic FeII porphyrins were used to catalyze indole dioxygenation, but the formation of μ-oxo-bridged FeIII–O–FeIII caused catalyst deactivation. Herein, we report a homogeneous electro-driven strategy to realize catalytic indole dioxygenation by Fe tetra(pentafluorophenyl)porphyrin with a turnover number up to 8825 and Faradaic efficiency exceeding 104%. In homogeneous catalysis, inert FeIII–O–FeIII, which is generated upon the oxidation of FeII porphyrin by FeIII-superoxo and/or FeIV═O, can be electrochemically reduced to FeII porphyrin to reinitiate catalysis. Moreover, we identified an intermediate formed between FeIII-superoxo and dimethylindole by in situ electrochemical mass spectrometry.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"112 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506451","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：