Catalysis Science & Technology最新文献

{"title":"A DFT mechanistic study on nickel-catalyzed arylation of amino alcohols with aryl electrophiles: insights into the origins of chemoselectivity†","authors":"Chao Shan ,&nbsp;Zhiqiang Zhang ,&nbsp;Junyan You ,&nbsp;Ranran Li ,&nbsp;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}

{"title":"Strongly coupled Ag/Cu with MXene for efficient tandem nitrate reduction reaction and zinc–nitrate batteries†","authors":"Bin Kui ,&nbsp;Shuang Zhao ,&nbsp;Yunhong Hu ,&nbsp;Kai Zheng ,&nbsp;Yuanhui Yao ,&nbsp;Song Chen ,&nbsp;Nana Wang ,&nbsp;Peng Gao ,&nbsp;Zhongchao Bai ,&nbsp;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^<em>δ</em>+/Cu^<em>δ</em>+, which preferentially catalyzes NO₃⁻ → NO₂⁻ and NO₂⁻ → NH₃ conversions, respectively. The synthesized Ag/Cu/MXene composite sample achieves an ammonia yield rate of 10.3 mol g_cat.⁻¹ h⁻¹ 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⁻², 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}

{"title":"Fe, Co, and Ni co-doped nitrogen-doped carbon nanotubes for the electrocatalytic oxygen reduction reaction†","authors":"Haitao Huang ,&nbsp;Zhijie Chen ,&nbsp;Haijin Li ,&nbsp;Yongtao Li ,&nbsp;Xiaolong Deng","doi":"10.1039/d4cy01507j","DOIUrl":"10.1039/d4cy01507j","url":null,"abstract":"<div><div>The creation of efficient non-precious metals is crucial for advancing electrochemical systems used in energy conversion and storage technologies. This work introduces an exceptionally potent and durable electrocatalyst, a trimetallic nitrogen-enriched carbon nanotube composite (FeCoNi@CNTs-NC-2), synthesized through a process of pyrolysis followed by acid treatment. Electrochemical tests have demonstrated that this catalyst displays remarkable performance and longevity in facilitating the oxygen reduction reaction. Furthermore, when integrated into Zn–air batteries, it delivers outstanding open-circuit voltage, power output, and specific energy capacity. These discoveries offer valuable insights for the engineering of effective and reliable electrocatalysts based on non-precious metal alloys.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1238-1246"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430667","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}

{"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 ,&nbsp;Zaman Abdalhussein Ibadi Alaridhee ,&nbsp;Rafid Kamal Jameel ,&nbsp;Morug Salih Mahdi ,&nbsp;Aseel Salah Mansoor ,&nbsp;Usama Kadem Radi ,&nbsp;Ameer Hassan Idan ,&nbsp;Hala Bahai ,&nbsp;Elyor Berdimurodov ,&nbsp;Ilyos Eliboev ,&nbsp;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 (CO₂) . This study focuses on using Mg nanoparticle-catalyzed graphene oxide modified with Prl-tacd@Mg, with a surface area of 95.3 [m² g⁻¹] 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}

{"title":"Surface-enhanced Raman scattering technique for comprehensive group-based structural identification of coke deposits on deactivated zeolite catalysts†","authors":"Guoliang Wu ,&nbsp;Qiang Bao ,&nbsp;Jian Zhang ,&nbsp;Mingjian Luo ,&nbsp;Zhirui Chen ,&nbsp;Xue Qiao ,&nbsp;Yi Hu ,&nbsp;Wenlin Wang ,&nbsp;Yunfeng Hu","doi":"10.1039/d4cy01361a","DOIUrl":"10.1039/d4cy01361a","url":null,"abstract":"<div><div>A coke detection strategy based on iodide-modified Ag NPs was established coupled with the release and dispersion of coke species. This method can selectively acquire group-based structural characteristics of coke species deposited on industrially deactivated zeolite catalysts with strong fluorescence within complex systems.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1003-1008"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430621","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}

{"title":"Kinetics, quantum yield and mechanism of the decatungstate-catalyzed photooxidation of C–H hydrogen donors: role of the persistent radical effect†","authors":"Saba Didarataee ,&nbsp;Julia Ong ,&nbsp;Anastasiia Suprun ,&nbsp;Neeraj Joshi ,&nbsp;Juan C. Scaiano","doi":"10.1039/d4cy01358a","DOIUrl":"10.1039/d4cy01358a","url":null,"abstract":"<div><div>We report absolute rate constants for the reaction of triplet decatungstate (³DT*) with hydroperoxides using laser techniques and taking advantage of its recently discovered NIR phosphorescence. This allows an understanding of kinetic and mechanistic details on ³DT* catalyzed oxidation, and the role of O₂ and hydroperoxides. We find that the DTH· radical is less reactive towards oxygen than usually assumed. We find that temporary accumulation of DTH· enables the persistent free radical mechanism to operate making DTH· an excellent disproportionation partner, which likely contributes to the good selectivity frequently observed when DT is used as a photoredox catalyst.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1149-1156"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430646","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}

{"title":"Catalytic hydrodenitrogenation of primary, secondary, and tertiary C12-alkyl amines over a platinum on zirconia catalyst†","authors":"Leoni-Franziska Klingelhöfer ,&nbsp;Joakim Kattelus ,&nbsp;Emma Verkama ,&nbsp;Jorge A. Velasco ,&nbsp;Leonhard Iser ,&nbsp;Marcus Rose ,&nbsp;Reetta Karinen ,&nbsp;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/ZrO₂ 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}

{"title":"Chlorine tailored CdOxCly/Al2O3 for syngas formation in electrochemical CO2 reduction†","authors":"Xin Wang ,&nbsp;Zhen-Hong He ,&nbsp;Hui-Hui Cao ,&nbsp;Yu-Xuan Ji ,&nbsp;Xuan-Lu Fan ,&nbsp;Rui-Peng Yan ,&nbsp;Kuan Wang ,&nbsp;Weitao Wang ,&nbsp;Lu Li ,&nbsp;Zhao-Tie Liu","doi":"10.1039/d4cy01426j","DOIUrl":"10.1039/d4cy01426j","url":null,"abstract":"<div><div>Electrocatalytic carbon dioxide reduction (eCO₂RR) 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 eCO₂RR to syngas over a CdO_<em>x</em>Cl_<em>y</em>/Al₂O₃ nanorod catalyst (denoted as CdO_<em>x</em>Cl_<em>y</em>/Al₂O₃ NRs) in an H-type cell. The results showed that the catalyst provides an adjustable H₂/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⁻² at a potential of −1.4 V (<em>vs.</em> RHE) in 0.5 M KHCO₃ 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 eCO₂RR 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}

{"title":"Direct C–N coupling of aniline to aminodiphenylamines with a platinum-loaded titanium oxide photocatalyst†","authors":"Kexin Zou ,&nbsp;Akira Yamamoto ,&nbsp;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/TiO₂) photocatalyst. A nearly 20% yield and 77% selectivity were achieved with the Pt/TiO₂ 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 &gt; 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 sp³ 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 TiO₂ photocatalyst excited by UV light, the second one starts with one electron transfer from the N atom in aniline to Ti in TiO₂, 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}

{"title":"Operando X-ray absorption spectroscopic flow cell for electrochemical CO2 reduction: new insight into the role of copper species†","authors":"Santhosh K. Matam ,&nbsp;P. K. Sharma ,&nbsp;E. H. Yu ,&nbsp;C. Drivas ,&nbsp;M. D. Khan ,&nbsp;M. Wilding ,&nbsp;N. Ramanan ,&nbsp;D. Gianolio ,&nbsp;M. A. Isaacs ,&nbsp;S. Guan ,&nbsp;P. R. Davies ,&nbsp;C. Richard A. Catlow","doi":"10.1039/d4cy00602j","DOIUrl":"10.1039/d4cy00602j","url":null,"abstract":"<div><div>We present a novel <em>operando</em> X-ray absorption spectroscopic (XAS) flow cell, consisting of a gas chamber for CO₂ and a liquid chamber for the electrolyte, to monitor electrochemical CO₂ reduction (eCO₂R) over a gas diffusion electrode (GDE). The feasibility of the flow cell is demonstrated by collecting XAS data (during eCO₂R over Cu-GDE) in a transmission mode at the Cu K-edge. The dynamic behaviour of copper during eCO₂R is captured by XAS, which is complemented by quasi <em>in situ</em> Raman and X-ray photoelectron spectroscopy (XPS). The linear combination analyses (LCA) of the X-ray absorption near edge structure (XANES) indicate that copper oxides are the only species present during the first 20 min of eCO₂R, which was corroborated by complementary Raman and XPS. Significantly, the complementary spectroscopic data suggest that the copper composition in the bulk and on the surface Cu-GDE evolve differently at and above 30 min of eCO₂R. LCA indicates that at 60 min, 77% of copper occurs as metallic Cu and the remaining 23% in the Cu(<span>ii</span>) oxidation state, which is not evident from the XPS results that show 100% of the copper is in &lt;2+ oxidation state. Thus, Cu(<span>ii</span>) is probably in the bulk of Cu-GDE, as is also evident from Raman spectroscopic result. The ethylene formation correlates very well with the occurrence of copper oxides and hydroxide species in Cu-GDE. The results not only demonstrate the applicability and versatility of the <em>operando</em> XAS GDE flow cell, but also illustrate the unique advantages of combining XAS with complementary Raman and XPS that enables the monitoring of the catalyst structural evolution from the bulk to surface and surface-adsorbed species.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1070-1081"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy00602j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430628","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}