Catalysis Science & Technology最新文献_第8页

Nature of molybdenum carbide surfaces for catalytic hydrogen dissociation using machine-learned potentials: an ensemble-averaged perspective†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-21 DOI: 10.1039/d4cy01202j

Woodrow N. Wilson , John Michael Lane , Chinmoy Saha , Sony Severin , Vivek S. Bharadwaj , Neeraj Rai

{"title":"Nature of molybdenum carbide surfaces for catalytic hydrogen dissociation using machine-learned potentials: an ensemble-averaged perspective†","authors":"Woodrow N. Wilson , John Michael Lane , Chinmoy Saha , Sony Severin , Vivek S. Bharadwaj , Neeraj Rai","doi":"10.1039/d4cy01202j","DOIUrl":"10.1039/d4cy01202j","url":null,"abstract":"<div><div>Molybdenum carbides with an electronic structure similar to noble metals have gained attention as a promising low-cost catalyst for biomass valorization and the hydrogen evolution reaction. However, our fundamental understanding of the catalyst surface and how different phases of these catalysts behave at varying reaction conditions is limited to ground state density functional theory calculations as <em>ab initio</em> molecular dynamics (AIMD) is computationally prohibitive at relevant length and time scales. In this work, we train a multi-atomic cluster expansion (MACE) machine-learned interatomic potentials (MLIP) to study hydrogen dissociation and dynamics over Mo, <em>δ</em>-MoC, α-Mo<sub>2</sub>C, and β-Mo<sub>2</sub>C surfaces at varying temperatures and hydrogen partial pressures. Our simulations identify unique and different molecular and atomic hydrogen adsorption sites on different surfaces that do not depend on the temperature. At low hydrogen pressures, the surface coverage is monolayer, which transitions to two-layer adsorption at higher pressures. We find that atomic hydrogen diffusion and recombinations are preferred over molybdenum atom hollow sites, while the diffusion over carbon-terminated facets was negligible, signifying particularly strong C–H interactions. In contrast, molecular hydrogen adsorption occurs mostly atop Mo or the bridging sites. At a comparable hydrogen loading, β-Mo<sub>2</sub>C (001) is the most active surface for hydrogen dissociation reaction. This work provides insights into the dynamic nature of the hydrogen dissociation chemistry and the diversity of hydrogen adsorption sites on molybdenum carbides.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 5","pages":"Pages 1492-1505"},"PeriodicalIF":4.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

A DFT mechanistic study on nickel-catalyzed arylation of amino alcohols with aryl electrophiles: insights into the origins of chemoselectivity†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-21 DOI: 10.1039/d4cy01460j

Chao Shan , Zhiqiang Zhang , Junyan You , Ranran Li , Xuexiang Ma

{"title":"A DFT mechanistic study on nickel-catalyzed arylation of amino alcohols with aryl electrophiles: insights into the origins of chemoselectivity†","authors":"Chao Shan , Zhiqiang Zhang , Junyan You , Ranran Li , Xuexiang Ma","doi":"10.1039/d4cy01460j","DOIUrl":"10.1039/d4cy01460j","url":null,"abstract":"<div><div>Nickel-catalyzed cross-couplings of alcohols/amines with aryl halides enable the challenging chemoselective <em>O</em>- or <em>N</em>-arylation of complex substrates concurrently containing competitive NH and OH moieties. Here, the reaction mechanisms and origins of the selective arylation of isolated alcohols or amines and amino alcohols with electrophiles were investigated using DFT calculations. The reaction proceeds sequentially through oxidative addition, anion exchange, and reductive elimination to produce the final product. Reductive elimination is the rate- and chemoselectivity-determining step of the overall reaction, and the energy differences of reductive elimination transition states can quantitatively rationalize the experimental results of chemoselectivity. The steric effect is the main factor regulating <em>N</em>- or <em>O</em>-arylation for competitive alcohols and alkylamines, while the electronic effect and steric effect jointly govern the <em>N</em>-arylation selectivity for competitive alcohols and arylamines. Furthermore, regarding the selective <em>O</em>-arylation of amino alcohols, the chemoselectivity originates from the smaller distortion of the substrate and catalyst, the stronger interaction between the lone pair electron n(O) and the vacant σ*(Ni–C) orbital, and the larger C–O non-covalent interaction strength. These insights into the factors regulating chemoselectivity will enable the development of selective arylation methods for complex substrates with competing nucleophilic sites.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 5","pages":"Pages 1634-1643"},"PeriodicalIF":4.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535667","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Strongly coupled Ag/Cu with MXene for efficient tandem nitrate reduction reaction and zinc–nitrate batteries†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-21 DOI: 10.1039/d4cy01511h

Bin Kui , Shuang Zhao , Yunhong Hu , Kai Zheng , Yuanhui Yao , Song Chen , Nana Wang , Peng Gao , Zhongchao Bai , Wei Ye

{"title":"Strongly coupled Ag/Cu with MXene for efficient tandem nitrate reduction reaction and zinc–nitrate batteries†","authors":"Bin Kui , Shuang Zhao , Yunhong Hu , Kai Zheng , Yuanhui Yao , Song Chen , Nana Wang , Peng Gao , Zhongchao Bai , Wei Ye","doi":"10.1039/d4cy01511h","DOIUrl":"10.1039/d4cy01511h","url":null,"abstract":"<div><div>The electrochemical conversion of nitrate ions into valuable ammonia represents a sustainable alternative to the traditional Haber–Bosch process. However, ammonia electrosynthesis from nitrate reduction is still limited by the low catalytic activity and faradaic efficiency. This work puts forward a two-step tandem strategy for nitrate reduction to ammonia by integrating charge polarized Ag nanoparticles and Cu nanoclusters on MXene to boost the electrocatalytic performance. The strongly coupled Ag nanoparticles/Cu clusters with MXene result in polarized Ag<sup><em>δ</em>+</sup>/Cu<sup><em>δ</em>+</sup>, which preferentially catalyzes NO<sub>3</sub><sup>−</sup> → NO<sub>2</sub><sup>−</sup> and NO<sub>2</sub><sup>−</sup> → NH<sub>3</sub> conversions, respectively. The synthesized Ag/Cu/MXene composite sample achieves an ammonia yield rate of 10.3 mol g<sub>cat.</sub><sup>−1</sup> h<sup>−1</sup> and a faradaic efficiency of 87.7% at −1.0 V <em>versus</em> a reversible hydrogen electrode, as well as good cycling stability. The composite was assembled into a zinc–nitrate battery as the cathode; the open-circuit voltage of the battery reaches 1.81 V, with a maximum output power density of 5.75 mW cm<sup>−2</sup>, demonstrating potential application value.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 5","pages":"Pages 1617-1626"},"PeriodicalIF":4.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Fe, Co, and Ni co-doped nitrogen-doped carbon nanotubes for the electrocatalytic oxygen reduction reaction†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-20 DOI: 10.1039/d4cy01507j

Haitao Huang , Zhijie Chen , Haijin Li , Yongtao Li , Xiaolong Deng

引用次数: 0

Designing a reusable chiral SPE electrode with Mg nanoparticles on graphene oxide for efficient enantioselective Grignard carboxylation of (1-bromoethyl)benzenes in a deep eutectic solvent

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-20 DOI: 10.1039/d4cy01324g

Amer Alhaj Zen , Zaman Abdalhussein Ibadi Alaridhee , Rafid Kamal Jameel , Morug Salih Mahdi , Aseel Salah Mansoor , Usama Kadem Radi , Ameer Hassan Idan , Hala Bahai , Elyor Berdimurodov , Ilyos Eliboev , Abdulrahman A. Almehizia

{"title":"Designing a reusable chiral SPE electrode with Mg nanoparticles on graphene oxide for efficient enantioselective Grignard carboxylation of (1-bromoethyl)benzenes in a deep eutectic solvent","authors":"Amer Alhaj Zen , Zaman Abdalhussein Ibadi Alaridhee , Rafid Kamal Jameel , Morug Salih Mahdi , Aseel Salah Mansoor , Usama Kadem Radi , Ameer Hassan Idan , Hala Bahai , Elyor Berdimurodov , Ilyos Eliboev , Abdulrahman A. Almehizia","doi":"10.1039/d4cy01324g","DOIUrl":"10.1039/d4cy01324g","url":null,"abstract":"<div><div>Researchers have developed a novel electrode for the enantioselective electro-organic Grignard carboxylation of (1-bromoethyl)benzenes with carbon dioxide (CO<sub>2</sub>) . This study focuses on using Mg nanoparticle-catalyzed graphene oxide modified with Prl-tacd@Mg, with a surface area of 95.3 [m<sup>2</sup> g<sup>−1</sup>] which, when combined with a choline chloride acetamide (ChCl/Ac) deep eutectic solvent, significantly enhances electrochemical performance. The goal is to achieve high selectivity and efficiency in the carboxylation process, contributing to sustainable chemical transformations. This innovative approach allows for the electro-organic synthesis of (<em>R</em>)-2-phenylpropanoic acid derivatives at a current of 15 mA for 30 min at room temperature, achieving yields between 88% and 96%. The ChCl/Ac system serves as a cost-effective electrolyte and solvent, facilitating an increased reaction rate. The synthesized products were characterized through various analytical techniques, including melting point analysis, 1HNMR spectroscopy, and CHN composition analysis. The electrode's performance was thoroughly evaluated using techniques such as X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analysis, cyclic voltammetry (CV), and Fourier-transform infrared spectroscopy (FT-IR). Its affordability and environmentally friendly characteristics highlight its potential for advancing sustainable electro-organic synthesis processes.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1185-1202"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Surface-enhanced Raman scattering technique for comprehensive group-based structural identification of coke deposits on deactivated zeolite catalysts†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-20 DOI: 10.1039/d4cy01361a

Guoliang Wu , Qiang Bao , Jian Zhang , Mingjian Luo , Zhirui Chen , Xue Qiao , Yi Hu , Wenlin Wang , Yunfeng Hu

引用次数: 0

Kinetics, quantum yield and mechanism of the decatungstate-catalyzed photooxidation of C–H hydrogen donors: role of the persistent radical effect†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-20 DOI: 10.1039/d4cy01358a

Saba Didarataee , Julia Ong , Anastasiia Suprun , Neeraj Joshi , Juan C. Scaiano

引用次数: 0

Catalytic hydrodenitrogenation of primary, secondary, and tertiary C12-alkyl amines over a platinum on zirconia catalyst†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-20 DOI: 10.1039/d4cy01099j

Leoni-Franziska Klingelhöfer , Joakim Kattelus , Emma Verkama , Jorge A. Velasco , Leonhard Iser , Marcus Rose , Reetta Karinen , Riikka L. Puurunen

{"title":"Catalytic hydrodenitrogenation of primary, secondary, and tertiary C12-alkyl amines over a platinum on zirconia catalyst†","authors":"Leoni-Franziska Klingelhöfer , Joakim Kattelus , Emma Verkama , Jorge A. Velasco , Leonhard Iser , Marcus Rose , Reetta Karinen , Riikka L. Puurunen","doi":"10.1039/d4cy01099j","DOIUrl":"10.1039/d4cy01099j","url":null,"abstract":"<div><div>In this work, the hydrodenitrogenation (HDN) of a primary amine (dodecylamine), a secondary amine (didodecylamine), and a tertiary amine (tridodecylamine) over a Pt/ZrO<sub>2</sub> catalyst was compared in a batch reactor. The main product of the amine hydrotreating was dodecane, but significant amounts of secondary amine were also formed as an intermediate during HDN of the primary and the tertiary amine. It was found that the primary amine is the only species for which direct HDN is possible; HDN of the secondary amine thus proceeds through a primary amine intermediate and HDN of the tertiary amine involves formation of the secondary amine, which decomposes to the primary amine. Consequently, HDN of the tertiary and secondary amines is slower than that of the primary amine. Kinetic modeling indicated that bimolecular condensation reactions of the primary amine, as well as potentially of the primary amine and the secondary amine, have a significant effect on the HDN process. Formation of the secondary amine from the primary amine increases the initial conversion and nitrogen removal rate but appeared to slow down the overall rate of nitrogen removal. The results thus demonstrate how condensation reactions affect amine HDN, which has implications for catalyst design for HDN of renewable feeds containing aliphatic amines.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1259-1271"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy01099j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chlorine tailored CdOxCly/Al2O3 for syngas formation in electrochemical CO2 reduction† 在电化学二氧化碳还原过程中生成合成气的氯定制 CdOxCly/Al2O3†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-20 DOI: 10.1039/d4cy01426j

Xin Wang , Zhen-Hong He , Hui-Hui Cao , Yu-Xuan Ji , Xuan-Lu Fan , Rui-Peng Yan , Kuan Wang , Weitao Wang , Lu Li , Zhao-Tie Liu

{"title":"Chlorine tailored CdOxCly/Al2O3 for syngas formation in electrochemical CO2 reduction†","authors":"Xin Wang , Zhen-Hong He , Hui-Hui Cao , Yu-Xuan Ji , Xuan-Lu Fan , Rui-Peng Yan , Kuan Wang , Weitao Wang , Lu Li , Zhao-Tie Liu","doi":"10.1039/d4cy01426j","DOIUrl":"10.1039/d4cy01426j","url":null,"abstract":"<div><div>Electrocatalytic carbon dioxide reduction (eCO<sub>2</sub>RR) is widely recognized as one of the most promising approaches to produce valuable chemicals especially syngas and mitigate carbon emissions. Hence, it holds immense significance to develop novel catalysts with exceptional efficiency and stability. In the present work, we presented the eCO<sub>2</sub>RR to syngas over a CdO<sub><em>x</em></sub>Cl<sub><em>y</em></sub>/Al<sub>2</sub>O<sub>3</sub> nanorod catalyst (denoted as CdO<sub><em>x</em></sub>Cl<sub><em>y</em></sub>/Al<sub>2</sub>O<sub>3</sub> NRs) in an H-type cell. The results showed that the catalyst provides an adjustable H<sub>2</sub>/CO ratio over a wide potential range of −1.0 V to −1.4 V (<em>vs.</em> RHE). The current density reached 59 mA cm<sup>−2</sup> at a potential of −1.4 V (<em>vs.</em> RHE) in 0.5 M KHCO<sub>3</sub> electrolyte. The introduction of chlorine increased the conductivity of the catalyst and promoted the electron transfer, which was further conducive to the production of CO. The preparation strategy of catalysts has important guiding significance for the design and preparation of catalysts with high efficiency in the eCO<sub>2</sub>RR to syngas.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1082-1089"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Direct C–N coupling of aniline to aminodiphenylamines with a platinum-loaded titanium oxide photocatalyst†

IF 4.4 3区化学

Catalysis Science & Technology Pub Date : 2025-01-20 DOI: 10.1039/d4cy01413h

Kexin Zou , Akira Yamamoto , Hisao Yoshida

{"title":"Direct C–N coupling of aniline to aminodiphenylamines with a platinum-loaded titanium oxide photocatalyst†","authors":"Kexin Zou , Akira Yamamoto , Hisao Yoshida","doi":"10.1039/d4cy01413h","DOIUrl":"10.1039/d4cy01413h","url":null,"abstract":"<div><div>Aminodiphenylamines (ADPAs) and their derivatives have been known to be used as dye intermediates and antioxidants of rubber. Due to their high demand in industrial production, their synthesis methods have been widely developed. In the present study, a photocatalytic asymmetric homocoupling route was examined, <em>i.e.</em>, the photocatalytic C–N coupling of aniline in an alkaline solution with a Pt-loaded titanium oxide (Pt/TiO<sub>2</sub>) photocatalyst. A nearly 20% yield and 77% selectivity were achieved with the Pt/TiO<sub>2</sub> photocatalyst for 30 min. It was found that this C–N bond formation showed a high dependence on the pH of the solvent and irradiation light wavelength, <em>i.e.</em>, the reaction can only proceed when pH > 11.79, and an incident light wavelength of 365 nm gave a high ADPA selectivity. The mechanistic studies by using isotopic compounds suggested that the rate-determining step (RDS) for ADPA production would be the formation of a transition complex with rehybridization to sp<sup>3</sup> on the aromatic ring of aniline. The UV-vis spectral analysis and Arrhenius plots further revealed the presence of three formation routes of ADPAs in the present system: the first one begins with the hole-oxidation of aniline by the TiO<sub>2</sub> photocatalyst excited by UV light, the second one starts with one electron transfer from the N atom in aniline to Ti in TiO<sub>2</sub>, which only occurred with an incident light wavelength of 365 nm, and the last one is the oxidation of aniline molecules by hydroxyl radicals as a minor route.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1228-1237"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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