Subnanometal catalysts usually possess significant catalytic performance due to their unique ″finite size effect″. The nanoengineering of copper (Cu) catalysts is a crucial approach for CO2 electroreduction (CO2ER) toward multicarbon (C2+) products. However, whether subnano-Cu clusters (0.5–2 nm) are a forbidden or promising zone for C2+ products through CO2ER remains controversial. To shed light on the feasibility and potential of Cu subnanoclusters as catalysts for CO2ER toward C2+ products, we employ global optimization by Revised Particle Swarm Optimization algorithm, density functional theory calculations, and microkinetic modeling on a range of Cu subnanoclusters with varying sizes to investigate CO2ER reactivity. We propose a geometric–electronic composite structural descriptor that characterizes the reaction energies and construct a theoretical reaction rate contour map based on the structural descriptor. The contour map reveals that Cu sites, reaching an optimal balance between the C–C coupling energy barrier and coverage of the coupling precursor, tend to exhibit high C2H4 yield. Furthermore, a volcano-like trend is presented between the theoretical turnover frequency of C2H4 products and the size of subnanoclusters, which is experimentally validated. Notably, medium-sized Cu subnanoclusters (around 1 nm) possessing the highest proportion of edge sites with the optimal value of structural descriptor own superior C2H4 yield to the large particles or monocrystal Cu catalysts in experiments. This work represents the first theoretical confirmation regarding the feasibility of subnano-Cu clusters in CO2RR for C2+ production and provides insights into its underlying mechanisms. These findings expand the field in size-dependent reactivity of Cu catalysts toward C2+ products through CO2ER and provide guidance for designing efficient Cu electrocatalysts at the subnanoscale.
{"title":"Revisits the Selectivity toward C2+ Products for CO2 Electroreduction over Subnano-Copper Clusters Based on Structural Descriptors","authors":"Xuning Wang, Yuqi Wang, Haoxiang Xu, Daojian Cheng","doi":"10.1021/acscatal.4c07759","DOIUrl":"https://doi.org/10.1021/acscatal.4c07759","url":null,"abstract":"Subnanometal catalysts usually possess significant catalytic performance due to their unique ″finite size effect″. The nanoengineering of copper (Cu) catalysts is a crucial approach for CO<sub>2</sub> electroreduction (CO<sub>2</sub>ER) toward multicarbon (C<sub>2+</sub>) products. However, whether subnano-Cu clusters (0.5–2 nm) are a forbidden or promising zone for C<sub>2+</sub> products through CO<sub>2</sub>ER remains controversial. To shed light on the feasibility and potential of Cu subnanoclusters as catalysts for CO<sub>2</sub>ER toward C<sub>2+</sub> products, we employ global optimization by Revised Particle Swarm Optimization algorithm, density functional theory calculations, and microkinetic modeling on a range of Cu subnanoclusters with varying sizes to investigate CO<sub>2</sub>ER reactivity. We propose a geometric–electronic composite structural descriptor that characterizes the reaction energies and construct a theoretical reaction rate contour map based on the structural descriptor. The contour map reveals that Cu sites, reaching an optimal balance between the C–C coupling energy barrier and coverage of the coupling precursor, tend to exhibit high C<sub>2</sub>H<sub>4</sub> yield. Furthermore, a volcano-like trend is presented between the theoretical turnover frequency of C<sub>2</sub>H<sub>4</sub> products and the size of subnanoclusters, which is experimentally validated. Notably, medium-sized Cu subnanoclusters (around 1 nm) possessing the highest proportion of edge sites with the optimal value of structural descriptor own superior C<sub>2</sub>H<sub>4</sub> yield to the large particles or monocrystal Cu catalysts in experiments. This work represents the first theoretical confirmation regarding the feasibility of subnano-Cu clusters in CO<sub>2</sub>RR for C<sub>2+</sub> production and provides insights into its underlying mechanisms. These findings expand the field in size-dependent reactivity of Cu catalysts toward C<sub>2+</sub> products through CO<sub>2</sub>ER and provide guidance for designing efficient Cu electrocatalysts at the subnanoscale.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"65 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849889","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 : 2025-04-18DOI: 10.1021/acscatal.5c00837
Raluca Bianca Tomoiagă, Levente Csaba Nagy, Krisztina Boros, Mădălina Elena Moisă, László Csaba Bencze
The enzymatic synthesis of d-phenylalanines, important chiral building blocks for several pharmaceuticals and fine chemicals, has been widely explored. Their asymmetric synthesis of high atom economy and accessible prochiral starting materials is highly attractive, while the expanding toolbox of protein engineering facilitates access to biocatalysts tailored for these processes. Accordingly, this Review provides an overview of the protein engineering efforts of enzymes involved in the asymmetric synthetic pathways for d-phenylalanines. The engineering efforts on d-amino acid dehydrogenases, d-amino acid transaminases, and phenylalanine ammonia-lyases to produce d-phenylalanines are thoroughly examined, while their application in (chemo)enzymatic cascades is also discussed. For an improved efficiency of the cascades, the protein engineering of l-amino acid deaminases and/or l-amino acid oxidases for an increased transformation of phenylalanines is also addressed.
{"title":"Engineered Biocatalysts for the Asymmetric Synthesis of d-Phenylalanines","authors":"Raluca Bianca Tomoiagă, Levente Csaba Nagy, Krisztina Boros, Mădălina Elena Moisă, László Csaba Bencze","doi":"10.1021/acscatal.5c00837","DOIUrl":"https://doi.org/10.1021/acscatal.5c00837","url":null,"abstract":"The enzymatic synthesis of <span>d</span>-phenylalanines, important chiral building blocks for several pharmaceuticals and fine chemicals, has been widely explored. Their asymmetric synthesis of high atom economy and accessible prochiral starting materials is highly attractive, while the expanding toolbox of protein engineering facilitates access to biocatalysts tailored for these processes. Accordingly, this Review provides an overview of the protein engineering efforts of enzymes involved in the asymmetric synthetic pathways for <span>d</span>-phenylalanines. The engineering efforts on <span>d</span>-amino acid dehydrogenases, <span>d</span>-amino acid transaminases, and phenylalanine ammonia-lyases to produce <span>d</span>-phenylalanines are thoroughly examined, while their application in (chemo)enzymatic cascades is also discussed. For an improved efficiency of the cascades, the protein engineering of <span>l</span>-amino acid deaminases and/or <span>l</span>-amino acid oxidases for an increased transformation of phenylalanines is also addressed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"17 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849892","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 : 2025-04-18DOI: 10.1021/acscatal.4c06577
Xupo Liu, Jiashu Tang, Ye Chen, Xiangjia Song, Junpo Guo, Gongke Wang, Shixing Han, Xin Chen, Congcong Zhang, Shixue Dou, Huaiyu Shao, Deli Wang
Electrooxidation of biomass-derived 5-hydroxymethylfurfural (HMF) is a green and economically viable approach to produce the valuable chemical 2,5-furandicarboxylic acid (FDCA). Given the significance of this transformation, there is a pressing demand for efficient electrocatalysts to expedite the HMF electrooxidation. This article provides a comprehensive overview of the electrooxidation mechanisms, structure–property correlations, and optimization strategies for catalysts involved in converting HMF into FDCA. Initially, the selectivity of reaction pathways, electrooxidation mechanisms, and thermodynamic and kinetic principles governing HMF oxidation are discussed, along with strategies to hinder the competitive oxygen evolution reaction. Subsequently, the structure–property correlations of electrocatalysts based on precious metals and transition metals are introduced in detail, emphasizing the promotion effects of various metal elements on the HMF oxidation process. Furthermore, an in-depth analysis of performance optimization strategies for electrocatalysts is also conducted, including tailoring surface adsorption, regulating dehydrogenation, accelerating proton transfer, integrating catalytic sites, and regenerating active species. Additionally, we critically assess the current challenges faced in developing highly effective HMF electrooxidation catalysts and propose future directions for overcoming these obstacles. This review article aims to provide insightful inspiration for developing high-efficiency electrocatalysts to expedite biomass conversion applications.
{"title":"Refining Electrocatalyst Design for 5-Hydroxymethylfurfural Oxidation: Insights into Electrooxidation Mechanisms, Structure–Property Correlations, and Optimization Strategies","authors":"Xupo Liu, Jiashu Tang, Ye Chen, Xiangjia Song, Junpo Guo, Gongke Wang, Shixing Han, Xin Chen, Congcong Zhang, Shixue Dou, Huaiyu Shao, Deli Wang","doi":"10.1021/acscatal.4c06577","DOIUrl":"https://doi.org/10.1021/acscatal.4c06577","url":null,"abstract":"Electrooxidation of biomass-derived 5-hydroxymethylfurfural (HMF) is a green and economically viable approach to produce the valuable chemical 2,5-furandicarboxylic acid (FDCA). Given the significance of this transformation, there is a pressing demand for efficient electrocatalysts to expedite the HMF electrooxidation. This article provides a comprehensive overview of the electrooxidation mechanisms, structure–property correlations, and optimization strategies for catalysts involved in converting HMF into FDCA. Initially, the selectivity of reaction pathways, electrooxidation mechanisms, and thermodynamic and kinetic principles governing HMF oxidation are discussed, along with strategies to hinder the competitive oxygen evolution reaction. Subsequently, the structure–property correlations of electrocatalysts based on precious metals and transition metals are introduced in detail, emphasizing the promotion effects of various metal elements on the HMF oxidation process. Furthermore, an in-depth analysis of performance optimization strategies for electrocatalysts is also conducted, including tailoring surface adsorption, regulating dehydrogenation, accelerating proton transfer, integrating catalytic sites, and regenerating active species. Additionally, we critically assess the current challenges faced in developing highly effective HMF electrooxidation catalysts and propose future directions for overcoming these obstacles. This review article aims to provide insightful inspiration for developing high-efficiency electrocatalysts to expedite biomass conversion applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"75 5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846738","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 : 2025-04-18DOI: 10.1021/acscatal.4c07765
Yair Shahaf, Thierry K. Slot, Shaked Avidan, Jeffrey E. Dick, David Eisenberg
The Haber-Bosch process has provided an energy-intensive way to produce ammonia for over 100 years. However, alternative methods are required to lower pollution and enhance energy efficiency. Unfortunately, key mechanistic insights into the heterogeneous reduction of nitrogen and its intermediates are lacking. The nitrite reduction reaction (NO<sub>2</sub>RR) is an important electrochemical reaction in the nitrogen cycle, playing a significant role in ammonia-based energy storage and wastewater remediation. Although the NO<sub>2</sub>RR involves the transfer of multiple protons competing with the hydrogen evolution reaction (HER), the effect of the proton donor has not been investigated in heterogeneous electrocatalysis. We now present an electrochemical study of nitrite reduction in four buffer systems acting as proton donors: citrate, phosphate, 2-(<i>N</i>-morpholino)ethanesulfonic acid, and borate buffers. The chosen catalyst was a typical iron- and nitrogen-codoped carbon (FeNC) with atomically dispersed FeN<sub>4</sub> sites. All buffers except borate enhanced the NO<sub>2</sub>RR considerably, while the reduction mechanism was independent of buffer identity. The kinetics of the reaction depended more strongly on buffer concentration than on the <i></i><span style="color: inherit;"></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><msubsup><mrow><mi>NO</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>−</mo></mrow></msubsup></math>' role="presentation" style="position: relative;" tabindex="0"><nobr aria-hidden="true"><span style="width: 2.219em; display: inline-block;"><span style="display: inline-block; position: relative; width: 1.991em; height: 0px; font-size: 110%;"><span style="position: absolute; clip: rect(1.196em, 1001.99em, 2.616em, -999.997em); top: -2.156em; left: 0em;"><span><span><span style="display: inline-block; position: relative; width: 1.991em; height: 0px;"><span style="position: absolute; clip: rect(3.128em, 1001.42em, 4.151em, -999.997em); top: -3.974em; left: 0em;"><span><span style="font-family: STIXMathJax_Main;">NO</span></span><span style="display: inline-block; width: 0px; height: 3.98em;"></span></span><span style="position: absolute; clip: rect(3.412em, 1000.57em, 4.207em, -999.997em); top: -4.372em; left: 1.423em;"><span><span style="font-size: 70.7%; font-family: STIXMathJax_Main;">−</span></span><span style="display: inline-block; width: 0px; height: 3.98em;"></span></span><span style="position: absolute; clip: rect(3.355em, 1000.46em, 4.151em, -999.997em); top: -3.69em; left: 1.423em;"><span><span style="font-size: 70.7%; font-family: STIXMathJax_Main;">2</span></span><span style="display: inline-block; width: 0px; height: 3.98em;"></span></span></span></span></span><span style="display: inline-block; width: 0px; height: 2.162em;"></span></span></span><span style="di
{"title":"Buffer Effects on Nitrite Reduction Electrocatalysis","authors":"Yair Shahaf, Thierry K. Slot, Shaked Avidan, Jeffrey E. Dick, David Eisenberg","doi":"10.1021/acscatal.4c07765","DOIUrl":"https://doi.org/10.1021/acscatal.4c07765","url":null,"abstract":"The Haber-Bosch process has provided an energy-intensive way to produce ammonia for over 100 years. However, alternative methods are required to lower pollution and enhance energy efficiency. Unfortunately, key mechanistic insights into the heterogeneous reduction of nitrogen and its intermediates are lacking. The nitrite reduction reaction (NO<sub>2</sub>RR) is an important electrochemical reaction in the nitrogen cycle, playing a significant role in ammonia-based energy storage and wastewater remediation. Although the NO<sub>2</sub>RR involves the transfer of multiple protons competing with the hydrogen evolution reaction (HER), the effect of the proton donor has not been investigated in heterogeneous electrocatalysis. We now present an electrochemical study of nitrite reduction in four buffer systems acting as proton donors: citrate, phosphate, 2-(<i>N</i>-morpholino)ethanesulfonic acid, and borate buffers. The chosen catalyst was a typical iron- and nitrogen-codoped carbon (FeNC) with atomically dispersed FeN<sub>4</sub> sites. All buffers except borate enhanced the NO<sub>2</sub>RR considerably, while the reduction mechanism was independent of buffer identity. The kinetics of the reaction depended more strongly on buffer concentration than on the <i></i><span style=\"color: inherit;\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\" display=\"inline\"><msubsup><mrow><mi>NO</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>&#x2212;</mo></mrow></msubsup></math>' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\"><nobr aria-hidden=\"true\"><span style=\"width: 2.219em; display: inline-block;\"><span style=\"display: inline-block; position: relative; width: 1.991em; height: 0px; font-size: 110%;\"><span style=\"position: absolute; clip: rect(1.196em, 1001.99em, 2.616em, -999.997em); top: -2.156em; left: 0em;\"><span><span><span style=\"display: inline-block; position: relative; width: 1.991em; height: 0px;\"><span style=\"position: absolute; clip: rect(3.128em, 1001.42em, 4.151em, -999.997em); top: -3.974em; left: 0em;\"><span><span style=\"font-family: STIXMathJax_Main;\">NO</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: absolute; clip: rect(3.412em, 1000.57em, 4.207em, -999.997em); top: -4.372em; left: 1.423em;\"><span><span style=\"font-size: 70.7%; font-family: STIXMathJax_Main;\">−</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: absolute; clip: rect(3.355em, 1000.46em, 4.151em, -999.997em); top: -3.69em; left: 1.423em;\"><span><span style=\"font-size: 70.7%; font-family: STIXMathJax_Main;\">2</span></span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span></span></span></span><span style=\"display: inline-block; width: 0px; height: 2.162em;\"></span></span></span><span style=\"di","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"108 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846735","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 : 2025-04-18DOI: 10.1021/acscatal.4c07149
Jordan Santiago Martinez, Luigi Carpisassi, Gonzalo Egea, Jaime Mazarío, Christian Wittee Lopes, Carmen Mora-Moreno, Susana Trasobares, Luigi Vaccaro, Jose Juan Calvino, Giovanni Agostini, Pascual Oña-Burgos
This study investigates the structure and catalytic properties of bimetallic nanocomposites derived from PdCo- and PdMn-based metal–organic frameworks. These materials, synthesized via chemical (Q) and thermal treatments (T), resulted in PdCo-QT and PdMn-QT catalysts containing Pd-based nanoparticles modified with Co or Mn and supported on N-doped carbon. Detailed characterization techniques confirm these complex structures, including high-resolution transmission electron microscopy, scanning transmission electron microscopy energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. The catalytic performances of these materials were evaluated for the selective semihydrogenation of phenylacetylene and 4-octyne under soft conditions (1 H2 bar, room temperature) in batch reactors, demonstrating very high selectivity (≥95 mol %) toward alkenes at high conversion levels (≥94 mol %). Moreover, they displayed significant stability after five catalytic cycles with minimal leaching and highly competitive values of alkyne productivity in the semihydrogenation of phenylacetylene. The study also explored the potential of these catalysts in continuous gas-phase reactions, where PdCo-QT demonstrated remarkable catalytic activity and selectivity with a high gas hourly space velocity.
{"title":"MOF-Derived PdCo and PdMn Systems as Versatile Catalysts in Alkyne Semihydrogenation","authors":"Jordan Santiago Martinez, Luigi Carpisassi, Gonzalo Egea, Jaime Mazarío, Christian Wittee Lopes, Carmen Mora-Moreno, Susana Trasobares, Luigi Vaccaro, Jose Juan Calvino, Giovanni Agostini, Pascual Oña-Burgos","doi":"10.1021/acscatal.4c07149","DOIUrl":"https://doi.org/10.1021/acscatal.4c07149","url":null,"abstract":"This study investigates the structure and catalytic properties of bimetallic nanocomposites derived from PdCo- and PdMn-based metal–organic frameworks. These materials, synthesized via chemical (Q) and thermal treatments (T), resulted in <b>PdCo-QT</b> and <b>PdMn-QT</b> catalysts containing Pd-based nanoparticles modified with Co or Mn and supported on N-doped carbon. Detailed characterization techniques confirm these complex structures, including high-resolution transmission electron microscopy, scanning transmission electron microscopy energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. The catalytic performances of these materials were evaluated for the selective semihydrogenation of phenylacetylene and 4-octyne under soft conditions (1 H<sub>2</sub> bar, room temperature) in batch reactors, demonstrating very high selectivity (≥95 mol %) toward alkenes at high conversion levels (≥94 mol %). Moreover, they displayed significant stability after five catalytic cycles with minimal leaching and highly competitive values of alkyne productivity in the semihydrogenation of phenylacetylene. The study also explored the potential of these catalysts in continuous gas-phase reactions, where <b>PdCo-QT</b> demonstrated remarkable catalytic activity and selectivity with a high gas hourly space velocity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846734","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 : 2025-04-18DOI: 10.1021/acscatal.4c07228
Josepha J.G. Kromwijk, Job G.A. Vloedgraven, Fleur Neijenhuis, Ward van der Stam, Matteo Monai, Bert M. Weckhuysen
To improve the performance of zeolite-based catalysts for the methane dehydroaromatization (MDA) reaction, it is of importance to understand the nature of the catalytically active phase. Although many studies have been devoted to unraveling the structure of the active site, there is still no consensus. Monomeric, dimeric, and/or clusters of molybdenum oxide or tungsten oxide are proposed precatalyst structures. This precatalyst is activated under reaction conditions, to form (oxy)carbidic species which are believed to be the active site. In this study, we investigated the effect of tungsten dispersion on the activation of W/ZSM-5 catalysts. We observed unexpected long activation times that could be shortened by inert or reductive pretreatment. Based on our investigations, we hypothesize that W/ZSM-5 catalysts with low weight loadings (i.e., 2 wt %) cannot be activated due to the presence of monomeric tungsten. For catalysts with medium weight loadings (i.e., 5 and 7 wt %), restructuring of the tungsten is required for the formation of the active site, which can be achieved through performing a thermal pretreatment. For higher weight loadings (i.e., 10 wt %), reduction plays a key role in the activation of the catalyst. We show that the activation of the catalyst is impacted by the precatalyst structure. These insights aid in the development of suitable activation treatments which could save time and energy if the reaction would be performed at an industrial scale.
{"title":"Impact of Tungsten Loading on the Activation of Zeolite-Based Catalysts for Methane Dehydroaromatization","authors":"Josepha J.G. Kromwijk, Job G.A. Vloedgraven, Fleur Neijenhuis, Ward van der Stam, Matteo Monai, Bert M. Weckhuysen","doi":"10.1021/acscatal.4c07228","DOIUrl":"https://doi.org/10.1021/acscatal.4c07228","url":null,"abstract":"To improve the performance of zeolite-based catalysts for the methane dehydroaromatization (MDA) reaction, it is of importance to understand the nature of the catalytically active phase. Although many studies have been devoted to unraveling the structure of the active site, there is still no consensus. Monomeric, dimeric, and/or clusters of molybdenum oxide or tungsten oxide are proposed precatalyst structures. This precatalyst is activated under reaction conditions, to form (oxy)carbidic species which are believed to be the active site. In this study, we investigated the effect of tungsten dispersion on the activation of W/ZSM-5 catalysts. We observed unexpected long activation times that could be shortened by inert or reductive pretreatment. Based on our investigations, we hypothesize that W/ZSM-5 catalysts with low weight loadings (i.e., 2 wt %) cannot be activated due to the presence of monomeric tungsten. For catalysts with medium weight loadings (i.e., 5 and 7 wt %), restructuring of the tungsten is required for the formation of the active site, which can be achieved through performing a thermal pretreatment. For higher weight loadings (i.e., 10 wt %), reduction plays a key role in the activation of the catalyst. We show that the activation of the catalyst is impacted by the precatalyst structure. These insights aid in the development of suitable activation treatments which could save time and energy if the reaction would be performed at an industrial scale.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846742","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}
Direct reduction of low–concentration CO2 in flue gas to multicarbon products has attracted increasing attention recently since it could reduce the high energy consumption of CO2 purification during CO2 recycling. Although various electrodes have been developed to convert diluted CO2 to different products, the changes in mechanisms due to the reduction of the CO2 concentration have rarely been studied. In this work, defective boron-modified copper electrodes were obtained for the direct conversion of diluted CO2 to dual carbon (C2) products. The Faradaic efficiency of C2 reached as high as 54.9%, even when the CO2 concentration was reduced to 25%. More importantly, the C–C coupling efficiency of *CO intermediates reached up to 79.3% under the condition of 25% CO2. This was attributed to the fact that a small amount of CO2 did not fully occupy all of the active sites at the beginning, which provided possible reaction space for the subsequent coupling and protonation reaction processes. Through in situ monitoring of different reaction intermediates under the conditions of different CO2 concentrations using in situ FT–IR, it is found that decreasing CO2 concentration did not alter the reaction pathway but influenced the conversion rate of key intermediates, which resulted in a change of product selectivity.
{"title":"Boosting the C–C Coupling Efficiency for Diluted CO2 Electroreduction to Dual Carbon Products","authors":"Ying Zhang, Qing Yu, Zhaolong Wang, Wei Zhang, Xiaojie She, Qiankang Zhang, Yunliang Liu, Haitao Li, Hui Xu","doi":"10.1021/acscatal.5c00090","DOIUrl":"https://doi.org/10.1021/acscatal.5c00090","url":null,"abstract":"Direct reduction of low–concentration CO<sub>2</sub> in flue gas to multicarbon products has attracted increasing attention recently since it could reduce the high energy consumption of CO<sub>2</sub> purification during CO<sub>2</sub> recycling. Although various electrodes have been developed to convert diluted CO<sub>2</sub> to different products, the changes in mechanisms due to the reduction of the CO<sub>2</sub> concentration have rarely been studied. In this work, defective boron-modified copper electrodes were obtained for the direct conversion of diluted CO<sub>2</sub> to dual carbon (C<sub>2</sub>) products. The Faradaic efficiency of C<sub>2</sub> reached as high as 54.9%, even when the CO<sub>2</sub> concentration was reduced to 25%. More importantly, the C–C coupling efficiency of *CO intermediates reached up to 79.3% under the condition of 25% CO<sub>2</sub>. This was attributed to the fact that a small amount of CO<sub>2</sub> did not fully occupy all of the active sites at the beginning, which provided possible reaction space for the subsequent coupling and protonation reaction processes. Through in situ monitoring of different reaction intermediates under the conditions of different CO<sub>2</sub> concentrations using in situ FT–IR, it is found that decreasing CO<sub>2</sub> concentration did not alter the reaction pathway but influenced the conversion rate of key intermediates, which resulted in a change of product selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849890","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 : 2025-04-18DOI: 10.1021/acscatal.5c00412
Manu Suvarna, Rubén Laplaza, Romain Graux, Núria López, Clémence Corminboeuf, Kjell Jorner, Javier Pérez-Ramírez
Volcano plots, stemming from the Sabatier principle, visualize descriptor–performance relationships, allowing rational catalyst design. Manually drawn volcanoes originating from experimental studies are potentially prone to human bias as no guidelines or metrics exist to quantify the goodness of fit. To address this limitation, we introduce a framework called SPOCK (systematic piecewise regression for volcanic kinetics) and validate it using experimental data from heterogeneous, homogeneous, and enzymatic catalysis to fit volcano-like relationships. We then generalize this approach to DFT-derived volcanoes and evaluate the tool’s robustness against noisy kinetic data and in identifying false-positive volcanoes, i.e., cases where studies claim a volcano-like relationship exists, but such correlations are not statistically significant. Once the SPOCK’s functional features are established, we demonstrate its potential to identify descriptor–performance relationships, exemplified via the ceria-promoted water–gas shift and single-atom-catalyzed electrocatalytic carbon dioxide reduction reactions. In both cases, the model uncovers descriptors previously unreported, revealing insights that are not easily recognized by human experts. Finally, we showcase SPOCK’s capabilities to formulate multivariable descriptors, an emerging topic in catalysis research. Our work pioneers an automated and standardized tool for volcano plot construction and validation, and we release the model as an open-source web application for greater accessibility and knowledge generation in catalysis.
{"title":"SPOCK Tool for Constructing Empirical Volcano Diagrams from Catalytic Data","authors":"Manu Suvarna, Rubén Laplaza, Romain Graux, Núria López, Clémence Corminboeuf, Kjell Jorner, Javier Pérez-Ramírez","doi":"10.1021/acscatal.5c00412","DOIUrl":"https://doi.org/10.1021/acscatal.5c00412","url":null,"abstract":"Volcano plots, stemming from the Sabatier principle, visualize descriptor–performance relationships, allowing rational catalyst design. Manually drawn volcanoes originating from experimental studies are potentially prone to human bias as no guidelines or metrics exist to quantify the goodness of fit. To address this limitation, we introduce a framework called SPOCK (systematic piecewise regression for volcanic kinetics) and validate it using experimental data from heterogeneous, homogeneous, and enzymatic catalysis to fit volcano-like relationships. We then generalize this approach to DFT-derived volcanoes and evaluate the tool’s robustness against noisy kinetic data and in identifying false-positive volcanoes, i.e., cases where studies claim a volcano-like relationship exists, but such correlations are not statistically significant. Once the SPOCK’s functional features are established, we demonstrate its potential to identify descriptor–performance relationships, exemplified via the ceria-promoted water–gas shift and single-atom-catalyzed electrocatalytic carbon dioxide reduction reactions. In both cases, the model uncovers descriptors previously unreported, revealing insights that are not easily recognized by human experts. Finally, we showcase SPOCK’s capabilities to formulate multivariable descriptors, an emerging topic in catalysis research. Our work pioneers an automated and standardized tool for volcano plot construction and validation, and we release the model as an open-source web application for greater accessibility and knowledge generation in catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846739","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}
Some oxidoreductases can communicate directly and electrically with electrodes; this process is called direct electron transfer (DET)-type bioelectrocatalysis. Understanding its detailed mechanisms is essential for developing and improving DET-based bioelectrochemical devices. In this study, we investigated the pH dependence of kinetic and thermodynamic characteristics of a variant of an aldehyde dehydrogenase (ALDH) without the cytochrome c subunit (ΔC_ALDH) and compared it with that of a wild-type recombinant ALDH (rALDH). Owing to the pronounced DET activity of ΔC_ALDH at multi-walled carbon nanotubes, the voltammograms were analyzed to obtain the enzymatic parameters. The potential difference between the electrode-active site of the enzyme and electron donor (E°′E – E°′D) and the limiting catalytic current density (jcat) exhibited an ideal linear free energy relationship (LFER), suggesting that the catalytic reaction of ΔC_ALDH was controlled by the thermodynamic driving force without any specific interactions. We also measured the ferricyanide reductase activity in solution (ksol) to investigate the effect of electron acceptors (electrode and ferricyanide) on the enzymatic properties. The ksol of ΔC_ALDH has a pH dependence similar to that of jcat; therefore, the experimental data were kinetically analyzed based on the LFER by considering the potential difference between the electron acceptor and electrode-active site of the enzyme (E°′A – E°′E). By integrating the analytical results obtained from the DET-type acetaldehyde oxidation using an electrode and ferricyanide reduction in solution, the catalytic constant for the DET-type bioelectrocatalysis (kDET) and the surface concentration of the effective enzyme immobilized on the electrode (ΓE,eff) of ΔC_ALDH were calculated to be 5000 ± 2000 s–1 and 13 ± 7 pmol cm–2, respectively. This study achieved a detailed evaluation of the multi-step catalytic reactions of redox enzymes and can help elucidate the reaction mechanisms of DET-type bioelectrocatalysis.
{"title":"Quantitative Elucidation of Catalytic Reaction of Truncated Aldehyde Dehydrogenase Based on Linear Free Energy Relationship","authors":"Konatsu Ichikawa, Taiki Adachi, Yuki Kitazumi, Osamu Shirai, Keisei Sowa","doi":"10.1021/acscatal.4c07978","DOIUrl":"https://doi.org/10.1021/acscatal.4c07978","url":null,"abstract":"Some oxidoreductases can communicate directly and electrically with electrodes; this process is called direct electron transfer (DET)-type bioelectrocatalysis. Understanding its detailed mechanisms is essential for developing and improving DET-based bioelectrochemical devices. In this study, we investigated the pH dependence of kinetic and thermodynamic characteristics of a variant of an aldehyde dehydrogenase (ALDH) without the cytochrome <i>c</i> subunit (ΔC_ALDH) and compared it with that of a wild-type recombinant ALDH (rALDH). Owing to the pronounced DET activity of ΔC_ALDH at multi-walled carbon nanotubes, the voltammograms were analyzed to obtain the enzymatic parameters. The potential difference between the electrode-active site of the enzyme and electron donor (<i>E</i>°′<sub>E</sub> – <i>E</i>°′<sub>D</sub>) and the limiting catalytic current density (<i>j</i><sub>cat</sub>) exhibited an ideal linear free energy relationship (LFER), suggesting that the catalytic reaction of ΔC_ALDH was controlled by the thermodynamic driving force without any specific interactions. We also measured the ferricyanide reductase activity in solution (<i>k</i><sub>sol</sub>) to investigate the effect of electron acceptors (electrode and ferricyanide) on the enzymatic properties. The <i>k</i><sub>sol</sub> of ΔC_ALDH has a pH dependence similar to that of <i>j</i><sub>cat</sub>; therefore, the experimental data were kinetically analyzed based on the LFER by considering the potential difference between the electron acceptor and electrode-active site of the enzyme (<i>E</i>°′<sub>A</sub> – <i>E</i>°′<sub>E</sub>). By integrating the analytical results obtained from the DET-type acetaldehyde oxidation using an electrode and ferricyanide reduction in solution, the catalytic constant for the DET-type bioelectrocatalysis (<i>k</i><sub>DET</sub>) and the surface concentration of the effective enzyme immobilized on the electrode (Γ<sub>E,eff</sub>) of ΔC_ALDH were calculated to be 5000 ± 2000 s<sup>–1</sup> and 13 ± 7 pmol cm<sup>–2</sup>, respectively. This study achieved a detailed evaluation of the multi-step catalytic reactions of redox enzymes and can help elucidate the reaction mechanisms of DET-type bioelectrocatalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"136 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846740","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}
Understanding the influence of oxygen vacancies is of great significance for revealing molecular adsorption and rational catalyst design. However, for the catalysts with multiple phases, the properties and intrinsic catalytic mechanism of oxygen vacancies on varied active sites have not been studied thoroughly. Herein, Zn–Cr catalysts with different oxygen vacancy distributions and contents are synthesized by engineering interfacial oxygen vacancies for CO2 hydrogenation. Characterization and DFT calculations illustrate that although the oxygen vacancies are not prone to being generated on the monointerface between ZnO and ZnCr2O4 compared with the spinel or metal oxide phases, the ZnO/ZnCr2O4–Ov interfacial oxygen vacancy sites reduce the energy barriers of crucial HCOO* and H3CO* intermediate formation for CH3OH synthesis. With the assistance of the well-dispersed interface oxygen vacancies, 3Zn1Cr displays the highest methanol selectivity (80.5%) as well as the highest CO2 conversion (19.2%) among all of the ratios of Zn–Cr catalysts. After further combination of 3Zn1Cr with modified β zeolite, the composite catalyst showed a superior liquefied petroleum gas selectivity of 84.0% at a CO2 conversion of 30.2%. The proposed strategy here sheds light on the efficient composite catalyst design via a methanol-mediated route for C1 chemistry.
{"title":"Engineering Interfacial Oxygen Vacancies of Zn–Cr Sites for CO2 Activation and Hydrogenation","authors":"Jiaming Liang, Lei Jiang, Hengyang Liu, Bowei Meng, Zhiliang Jin, Lisheng Guo, Zhihao Liu, Teng Li, Wenhang Wang, Chengwei Wang, Ying Shi, Guangbo Liu, Kai Sun, Yingluo He, Bing Liang, Noritatsu Tsubaki","doi":"10.1021/acscatal.5c00766","DOIUrl":"https://doi.org/10.1021/acscatal.5c00766","url":null,"abstract":"Understanding the influence of oxygen vacancies is of great significance for revealing molecular adsorption and rational catalyst design. However, for the catalysts with multiple phases, the properties and intrinsic catalytic mechanism of oxygen vacancies on varied active sites have not been studied thoroughly. Herein, Zn–Cr catalysts with different oxygen vacancy distributions and contents are synthesized by engineering interfacial oxygen vacancies for CO<sub>2</sub> hydrogenation. Characterization and DFT calculations illustrate that although the oxygen vacancies are not prone to being generated on the monointerface between ZnO and ZnCr<sub>2</sub>O<sub>4</sub> compared with the spinel or metal oxide phases, the ZnO/ZnCr<sub>2</sub>O<sub>4</sub>–O<sub>v</sub> interfacial oxygen vacancy sites reduce the energy barriers of crucial HCOO* and H<sub>3</sub>CO* intermediate formation for CH<sub>3</sub>OH synthesis. With the assistance of the well-dispersed interface oxygen vacancies, 3Zn1Cr displays the highest methanol selectivity (80.5%) as well as the highest CO<sub>2</sub> conversion (19.2%) among all of the ratios of Zn–Cr catalysts. After further combination of 3Zn1Cr with modified β zeolite, the composite catalyst showed a superior liquefied petroleum gas selectivity of 84.0% at a CO<sub>2</sub> conversion of 30.2%. The proposed strategy here sheds light on the efficient composite catalyst design via a methanol-mediated route for C1 chemistry.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"46 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849891","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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