ACS Catalysis 最新文献

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Accelerated Catalysis of Atomically Precise Thiolate-Protected Gold Nanoclusters by Supramolecular Ligand Engineering 超分子配体工程加速催化原子精确硫代酸保护金纳米团簇
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-09 DOI: 10.1021/acscatal.5c01743
Kyosuke Ueda, Ryohei Saito, Kenta Iseri, Sota Sekiya, Masaharu Nakamura, Katsuhiro Isozaki
{"title":"Accelerated Catalysis of Atomically Precise Thiolate-Protected Gold Nanoclusters by Supramolecular Ligand Engineering","authors":"Kyosuke Ueda, Ryohei Saito, Kenta Iseri, Sota Sekiya, Masaharu Nakamura, Katsuhiro Isozaki","doi":"10.1021/acscatal.5c01743","DOIUrl":"https://doi.org/10.1021/acscatal.5c01743","url":null,"abstract":"We herein report the reaction acceleration effect of a supramolecular reaction field constructed with dendritic peptide thiolate ligands on the Au<sub>25</sub> nanocluster toward the catalytic cyclization of alkynoic acids. A remarkable reaction acceleration was achieved by peptide dendron thiolate ligands, which was 40 times greater than that achieved by simple alkyl thiolate ligands. Association experiments with <sup>1</sup>H NMR spectroscopy revealed that the unprecedented intermolecular hydrogen bonds between peptide dendron ligands and ammonium salts of alkynoic acids play a critical role in the reaction acceleration effect. The high stability of the nanocluster catalyst bearing the supramolecular reaction field was also represented by the turnover number over 820,000 in this catalytic reaction. Mechanistic investigations revealed the involvement of pi-coordinated alkynes and subsequent vinyl–Au intermediates. DFT calculations support the possible reaction pathway, including both the anionic and neutral forms of the nanocluster as the catalyst. Our findings demonstrate the usefulness of the supramolecular ligand approach for metallic nanocluster catalysis, enabling enhanced catalytic efficiency and selectivity toward various organic transformations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Exploring the Structure and Function of Rare-Earth Elements Incorporated into Zeolite Catalysts 稀土元素掺入沸石催化剂的结构与功能研究
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-09 DOI: 10.1021/acscatal.5c02328
Mingze Zheng, Shivangi N. Borate, James W. Harris, Brandon C. Bukowski
{"title":"Exploring the Structure and Function of Rare-Earth Elements Incorporated into Zeolite Catalysts","authors":"Mingze Zheng, Shivangi N. Borate, James W. Harris, Brandon C. Bukowski","doi":"10.1021/acscatal.5c02328","DOIUrl":"https://doi.org/10.1021/acscatal.5c02328","url":null,"abstract":"Rare-earth element (REE) incorporation into dealuminated zeolites has been shown to catalyze a variety of selective oxygenate transformations, including ethanol to olefins, yet the structure and function of REE-incorporated Lewis acid zeotypes remain unclear. In this study, we proposed five yttrium acid site configurations and evaluated each against experimental physicochemical characterization techniques including X-ray absorption spectroscopy and pyridine Fourier transformed infrared spectroscopy (FTIR). Our analysis identified three fundamental site motifs, defect-open, dehydrated defect-open, and geminal hydroxyl, stabilized by adjacent silanol defects and hydroxyl groups that agreed with spectroscopic characterization. By comparing ethanol dehydration kinetics, we identified that interconvertible defect-open and dehydrated defect-open sites are kinetically relevant for catalytic turnovers. The three yttrium open site structural motifs from Y/deAlBeta were extended to 14 other REEs (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) to explore trends in Lewis acid strength, assessed via pyridine adsorption energies and supported by experimentally measured pyridine FTIR. A linear correlation between Lewis acid strength and highest occupied molecular orbital + lowest unoccupied molecular orbital energies was established, offering a predictive framework for understanding structure–function relationships in REEs incorporated into dealuminated Beta zeotypes. These findings provide molecular-level insight into REE incorporation and its role in tuning Lewis acid strength for the selective catalytic transformation of biomass-derived oxygenates into chemicals and liquid fuels.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enhanced Selectivity for C2H4 Production from C2H6 on Partially Chlorinated IrO2(110) Surfaces 部分氯化IrO2(110)表面上C2H6生成C2H4的选择性增强
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-09 DOI: 10.1021/acscatal.5c03179
Connor Pope, Jungwon Yun, Rishikishore Reddy, Jovenal Jamir, Minkyu Kim, Aravind Asthagiri, Jason F. Weaver
{"title":"Enhanced Selectivity for C2H4 Production from C2H6 on Partially Chlorinated IrO2(110) Surfaces","authors":"Connor Pope, Jungwon Yun, Rishikishore Reddy, Jovenal Jamir, Minkyu Kim, Aravind Asthagiri, Jason F. Weaver","doi":"10.1021/acscatal.5c03179","DOIUrl":"https://doi.org/10.1021/acscatal.5c03179","url":null,"abstract":"Modifying metal oxide surfaces to limit their oxidizing activity can provide a means of improving catalytic selectivity toward the partial oxidation of light alkanes. In this study, we investigated the oxidation of C<sub>2</sub>H<sub>6</sub> on Cl-modified IrO<sub>2</sub>(110) surfaces using temperature-programmed reaction spectroscopy (TPRS) and first-principles microkinetic modeling. We find that substituting Cl for O in the IrO<sub>2</sub>(110) surface enhances the selectivity for C<sub>2</sub>H<sub>6</sub> conversion to C<sub>2</sub>H<sub>4</sub> during TPRS by suppressing extensive oxidation to CO<sub> <italic toggle=\"yes\">x</italic> </sub> products, while also either enhancing C<sub>2</sub>H<sub>4</sub> production or altering it to a lesser extent, depending on the initial C<sub>2</sub>H<sub>6</sub> coverage. The C<sub>2</sub>H<sub>4</sub> selectivity increased with increasing C<sub>2</sub>H<sub>6</sub> and Cl coverage, but reached a limiting value below 50%. The Cl coverage changed negligibly during C<sub>2</sub>H<sub>6</sub> oxidation, and the surface reactivity decreased only marginally for Cl coverages up to 0.5 ML (monolayer). TPRS simulations using a microkinetic model predict C<sub>2</sub>H<sub>4</sub> and CO<sub> <italic toggle=\"yes\">x</italic> </sub> product yields as a function of the Cl coverage that agree closely with the experimental results. According to the simulations, C<sub>2</sub>H<sub>6</sub> conversion to C<sub>2</sub>H<sub>4</sub> occurs on Cl-IrO<sub>2</sub>(110) by the hydrogenation of C<sub>2</sub>H<sub>3</sub>* species adsorbed in blocked states, in which neighboring sites are occupied only by unreactive HO and Cl species. The microkinetic modeling shows that H-hopping away from surface HO groups provides a relatively efficient route for C<sub>2</sub>H<sub>3</sub>* to escape blocked configurations and dehydrogenate, and that this process can limit the C<sub>2</sub>H<sub>4</sub> selectivity on Cl-IrO<sub>2</sub>(110) under the conditions studied. Overall, our results demonstrate that Cl-substitution into IrO<sub>2</sub>(110) enhances the selectivity for C<sub>2</sub>H<sub>4</sub> production from C<sub>2</sub>H<sub>6</sub> and provides insights into the reaction mechanism that can guide strategies to further improve the C<sub>2</sub>H<sub>4</sub> selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"109 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
PtIn Alloy Supported on Y 2 O 3 ‑Modified δ‑Al 2 O 3 as a Propane Dehydrogenation Catalyst 改性δ - al2o3负载PtIn合金丙烷脱氢催化剂
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-08 DOI: 10.1021/acscatal.5c03103
Jilei Lin, Meiqing Shen, Sifeng Bi, Gurong Shen, Feng Gao, Wei Li
{"title":"PtIn Alloy Supported on Y 2 O 3 ‑Modified δ‑Al 2 O 3 as a Propane Dehydrogenation Catalyst","authors":"Jilei Lin, Meiqing Shen, Sifeng Bi, Gurong Shen, Feng Gao, Wei Li","doi":"10.1021/acscatal.5c03103","DOIUrl":"https://doi.org/10.1021/acscatal.5c03103","url":null,"abstract":"Propylene production via propane dehydrogenation (PDH) over supported platinum (Pt) catalysts is a vital industrial process. However, rapid catalyst deactivation due to coking necessitates periodic regeneration under harsh oxidative conditions. While alloying Pt with transition metals significantly reduces coking, these alloy catalysts often exhibit poor regeneration stability. In this study, we demonstrate that supporting PtIn nanoparticles on Y<sub>2</sub>O<sub>3</sub>-modified δ-Al<sub>2</sub>O<sub>3</sub> yields a PDH catalyst with significantly improved activity and stability. This catalyst achieves propane conversion rates close to the thermodynamic equilibrium at an ultralow Pt loading of 0.1 wt %, along with high propylene selectivity. Notably, this catalyst also exhibits remarkable regeneration stability. Through reaction-regeneration cycling experiments with various catalyst formulations, we reveal that the alloy effects between Pt and In are primarily responsible for enhanced catalyst stability under steady-state reaction conditions by suppressing coke formation. Meanwhile, the incorporation of Y<sub>2</sub>O<sub>3</sub> as a support component significantly improves stability during regeneration. Density functional theory (DFT) calculations further elucidate the key factors contributing to the enhanced anticoking properties of the catalyst under PDH reaction conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"84 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Machine-Learning-Driven Photocurrent Prediction in Multielement-Doped Hematite Photoelectrodes 机器学习驱动的多元素掺杂赤铁矿光电极的光电流预测
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-08 DOI: 10.1021/acscatal.5c02536
Takuma Nishimura, Yoshitaka Kumabe, Yosuke Harashima, Mikiya Fujii, Takashi Tachikawa
{"title":"Machine-Learning-Driven Photocurrent Prediction in Multielement-Doped Hematite Photoelectrodes","authors":"Takuma Nishimura, Yoshitaka Kumabe, Yosuke Harashima, Mikiya Fujii, Takashi Tachikawa","doi":"10.1021/acscatal.5c02536","DOIUrl":"https://doi.org/10.1021/acscatal.5c02536","url":null,"abstract":"Reliably predicting heterogeneous photocatalyst efficiency using machine learning (ML) remains challenging, because of variations in synthesis protocols and evaluation methods. To address this, we developed ML models to predict the photocurrent density, which is an indicator of the hydrogen generation rate in photoelectrochemical (PEC) water splitting. For multielement-doped hematite photoelectrodes, which have demonstrated potential for enhancing solar energy conversion, we acquired over 2000 data files uniformly and systematically from approximately 100 samples. A high predictive accuracy with a coefficient of determination (<italic toggle=\"yes\">R</italic> <sup>2</sup>) of 0.817 and a root mean squared error (RMSE) of 0.105 mA cm<sup>–2</sup> was achieved using elemental features and Raman spectra as explanatory variables. By analyzing this ML model, we identified both semiconductor properties and device characteristics as key factors for achieving high performance, particularly valence-related information, electron delocalization, and particle density on the substrate. Finally, we extrapolated the photocurrent densities for 79 800 virtual hematite samples doped with two or three elements using our high-precision ML model, revealing elements that could potentially enhance or reduce the PEC performance, while also predicting the performance of masked samples accurately. These findings establish a robust framework for data-driven materials discovery and rational dopant selection, thereby facilitating the optimization of hematite-based photoelectrodes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"151 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Efficient CO2 Electroreduction to CO on Chiral Nanostructured Au Films 手性纳米结构Au膜上CO2电还原成CO的研究
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-08 DOI: 10.1021/acscatal.5c01589
Wanning Zhang, Jiao Wang, Tianwei Ouyang, Lu Han, Yingying Duan, Shunai Che, Yuxi Fang
{"title":"Efficient CO2 Electroreduction to CO on Chiral Nanostructured Au Films","authors":"Wanning Zhang, Jiao Wang, Tianwei Ouyang, Lu Han, Yingying Duan, Shunai Che, Yuxi Fang","doi":"10.1021/acscatal.5c01589","DOIUrl":"https://doi.org/10.1021/acscatal.5c01589","url":null,"abstract":"The electroreduction of CO<sub>2</sub> to CO presents a promising strategy for converting CO<sub>2</sub> to value-added chemicals. However, achieving high Faradaic efficiency (FE) at elevated current densities is a persistent challenge, suffering from difficult activation of CO<sub>2</sub> and the high energy barrier for reaction intermediates. Herein, we propose that the spin-polarized chiral nanostructured Au films (CNAFs) can facilitate the activation of CO<sub>2</sub> over the surface with parallel electron spin alignment and utilize helical lattice distortions to reduce the energy barrier for the *COOH intermediate, leading to enhanced CO production. The CNAFs, characterized as helically twisted nanoflakes, were fabricated via electrodeposition using histidine as a symmetry-breaking agent. The CNAFs exhibited a maximum FE<sub>CO</sub> of ∼99% at −0.19 V vs the reversible hydrogen electrode (RHE), and an FE<sub>CO</sub> of ∼88% at a current density of ∼180 mA/cm<sup>2</sup> at −0.59 V vs RHE. Our findings elucidate the underlying mechanisms of CO<sub>2</sub> conversion, paving the way for the innovation of spin-polarized catalysts with specific defects.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
ZrO2 Morphology-Dependent Cu–ZrO2 Interfacial Catalysis in CO2 Hydrogenation to Methanol Reaction ZrO2形态依赖性Cu-ZrO2界面催化CO2加氢制甲醇反应
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-08 DOI: 10.1021/acscatal.5c01716
Jieqiong Ding, Dongdong Wang, Jialin Li, Weixin Huang
{"title":"ZrO2 Morphology-Dependent Cu–ZrO2 Interfacial Catalysis in CO2 Hydrogenation to Methanol Reaction","authors":"Jieqiong Ding, Dongdong Wang, Jialin Li, Weixin Huang","doi":"10.1021/acscatal.5c01716","DOIUrl":"https://doi.org/10.1021/acscatal.5c01716","url":null,"abstract":"In this study, we utilize monoclinic ZrO<sub>2</sub> with different morphologies, including nanoparticulate ZrO<sub>2</sub>, rod-like ZrO<sub>2</sub>, and star-like ZrO<sub>2</sub>, to investigate the ZrO<sub>2</sub> morphology effect on Cu–ZrO<sub>2</sub> interfacial catalysis in the CO<sub>2</sub> hydrogenation to methanol reaction. ZrO<sub>2</sub> morphology strongly affects the structures, adsorption behaviors, and catalytic performance of Cu/ZrO<sub>2</sub> catalysts. Various Cu/ZrO<sub>2</sub> catalysts show very different catalytic selectivities, although their catalytic activities are rather poor. Bridged (bri-HCOO*) and monodentate (m-HCOO*) formate species form on Cu/ZrO<sub>2</sub> catalysts during the CO<sub>2</sub> hydrogenation to methanol reaction. Elementary surface reaction kinetics analysis using temporal in situ DRIFTS in combination with online mass spectrometry reveals elementary reaction activation energies of 61.3 ± 5 kJ/mol for bri-HCOO* hydrogenation mainly to methanol and 85.0 ± 14 kJ/mol for m-HCOO* hydrogenation mainly to CO. Meanwhile, the apparent activation energy for CH<sub>3</sub>OH and CO formations from the CO<sub>2</sub> hydrogenation reaction catalyzed by Cu/nanoparticulate ZrO<sub>2</sub> is 65.7 ± 4 and 118.6 ± 14 kJ/mol, respectively. These results suggest that bri-HCOO* should be the formate intermediate for methanol production by CO<sub>2</sub> hydrogenation, and its hydrogenation reaction should be the rate-limiting step. Our findings clearly differentiate the reaction pathways of bri-HCOO* and m-HCOO* intermediates on Cu/ZrO<sub>2</sub> during the CO<sub>2</sub> hydrogenation to methanol reaction and demonstrate catalyst structural engineering in combination with elementary surface reaction kinetics analysis as a powerful strategy for fundamental studies of complex heterogeneous catalytic reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"6 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Amorphous–Crystalline Interface Coupling of IrNiOx/WO3 for Efficient and Stable Acidic Water Splitting IrNiOx/WO3的非晶界面耦合用于高效稳定的酸性水裂解
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-08 DOI: 10.1021/acscatal.5c02782
Huimin Zhang, Ping Song, Xuanhao Mei, Dezheng Zhang, Cong Liu, Mingtao Chu, Teng Zhang, Ce Han, Weilin Xu
{"title":"Amorphous–Crystalline Interface Coupling of IrNiOx/WO3 for Efficient and Stable Acidic Water Splitting","authors":"Huimin Zhang, Ping Song, Xuanhao Mei, Dezheng Zhang, Cong Liu, Mingtao Chu, Teng Zhang, Ce Han, Weilin Xu","doi":"10.1021/acscatal.5c02782","DOIUrl":"https://doi.org/10.1021/acscatal.5c02782","url":null,"abstract":"Developing an efficient and stable bifunctional electrocatalyst for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in acidic media is of great significance, yet remains challenging. Herein, a bifunctional electrocatalyst supported by carbon cloth, denoted as IrNiO<sub><i>x</i></sub>/WO<sub>3</sub>, was designed and synthesized through heterostructured coupling of active amorphous IrNiO<sub><i>x</i></sub> with stable crystalline WO<sub>3</sub>. Benefiting from the pronounced electron interaction stemming from the as-generated numerous heterointerfaces, as-fabricated IrNiO<sub><i>x</i></sub>/WO<sub>3</sub> demonstrates a low cell voltage of 1.539 V to achieve 10 mA cm<sup>–2</sup> for water splitting with a low Ir loading of 0.8 wt % while maintaining stability over 100 h of continuous electrolysis in 0.5 M H<sub>2</sub>SO<sub>4</sub>. Furthermore, through comprehensive structural characterization and theoretical analysis, it was revealed that the Ir sites in the Ir–O–Ni configuration within amorphous IrNiO<sub><i>x</i></sub> serve as the primary active sites for both HER and OER processes. Moreover, the corresponding energy barriers were found to be significantly lowered due to the strong electronic interaction between amorphous IrNiO<sub><i>x</i></sub> and crystalline WO<sub>3</sub>. This study provides a strategy for designing amorphous–crystalline heterostructured electrocatalysts with ideal interfacial properties for efficient overall water splitting.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"62 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Reductive Treatment of Ga–Pt-Supported Catalytically Active Liquid Metal Solutions (SCALMS) for Propane Dehydrogenation 丙烷脱氢中ga - pt负载催化活性液态金属溶液(SCALMS)的还原处理
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-07-08 DOI: 10.1021/acscatal.5c01463
Nnamdi Madubuko, Tzung-En Hsieh, Nora Vorlaufer, Simon Carl, Julien Steffen, Andreas Mölkner, Nicola Taccardi, Johannes Frisch, Regan G. Wilks, Johannes Will, Marco Haumann, Andreas Görling, Erdmann Spiecker, Peter Felfer, Marcus Bär, Peter Wasserscheid
{"title":"Reductive Treatment of Ga–Pt-Supported Catalytically Active Liquid Metal Solutions (SCALMS) for Propane Dehydrogenation","authors":"Nnamdi Madubuko, Tzung-En Hsieh, Nora Vorlaufer, Simon Carl, Julien Steffen, Andreas Mölkner, Nicola Taccardi, Johannes Frisch, Regan G. Wilks, Johannes Will, Marco Haumann, Andreas Görling, Erdmann Spiecker, Peter Felfer, Marcus Bär, Peter Wasserscheid","doi":"10.1021/acscatal.5c01463","DOIUrl":"https://doi.org/10.1021/acscatal.5c01463","url":null,"abstract":"A comprehensive investigation of the impact of hydrogen (H<sub>2</sub>) pretreatments on Ga–Pt supported catalytic active liquid metal solution (SCALMS) for propane dehydrogenation (PDH) is reported. Our approach bridges from model system investigations to real-world catalytic systems, which are tested in continuously operating PDH reactors. The microscopic and spectroscopic findings on model Ga–Pt systems suggest changes in the electronic structure and surface chemistry during SCALMS sample oxidation and H<sub>2</sub> pretreatment, indicating potential modifications of the active sites involved in PDH. H<sub>2</sub> pretreatments of technical Ga–Pt SCALMS prepared by ultrasonication (US) led to significantly improved activity, i.e., the conversion of propane increased from 10% for the untreated catalyst to 26% for the H<sub>2</sub> pretreated (5 h at 823 K) catalyst. We attribute this enhanced activity to the removal of a gallium oxide (GaO<sub> <italic toggle=\"yes\">x</italic> </sub>) shell, as confirmed by synchrotron-based in situ X-ray photoelectron spectroscopy (XPS) as well as in situ transmission electron microscopy (TEM) investigations of Ga–Pt model alloys. These findings are supported by density functional theory (DFT) and machine learned force field (ML-FF) calculations. Increasing the temperature of the H<sub>2</sub> treatment to 923 K reduced the deactivation rate of the catalyst to as low as 0.01 h<sup>–1</sup>, which is 3 times more stable than what was observed for the untreated catalyst. This deactivation is ascribed to bulk restructuring of the alloy, leading to the formation of less active Pt species as confirmed by spectroscopic and microscopic analysis. Our work not only elucidates the fundamental properties, i.e., typology, electronic structure, and reactivity, of isolated Pt atoms in Ga–Pt SCALMS but also proposes underlying mechanisms for the activation and deactivation of PDH catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"109 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Metal-Oxide Interface Sites Created Using Atomic Layer Deposition and Tested for CO Oxidation. 使用原子层沉积创建的金属氧化物界面位点和CO氧化测试。
IF 11.3 1区 化学
ACS Catalysis Pub Date : 2025-07-07 eCollection Date: 2025-07-18 DOI: 10.1021/acscatal.5c03164
Wang Ke, Ilkeun Lee, Francisco Zaera
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