Catalysis Science & Technology最新文献

{"title":"Exploration of the synergistic regulatory mechanism of hydroxide and fluoride modification on the photocatalytic activity of 2D g-C3N4†","authors":"Qianqian Shang ,&nbsp;Hongbing Wang ,&nbsp;Changjie Kan ,&nbsp;Rui Ding ,&nbsp;Yankai Li ,&nbsp;Shiva Pandeya ,&nbsp;Ziliang Li ,&nbsp;Mahesh Kumar Joshi","doi":"10.1039/d4cy00971a","DOIUrl":"10.1039/d4cy00971a","url":null,"abstract":"<div><div>Exfoliation and hetero-element doping are common procedures for band gap engineering and enhancing the photocatalytic properties of g-C₃N₄. A novel and facile strategy for simultaneous exfoliation and hetero-element doping is still in high demand. Herein, we prepared hydroxide and fluoride doped ultrathin g-C₃N₄ nanosheets through the single-step solvothermal exfoliation of bulk g-C₃N₄ (BCN) using varying concentrations of ethanol and hydrofluoric acid (HF). The microscopic and spectroscopic analysis confirmed the doping of hydroxide groups and fluoride groups (HO⁻/F⁻ groups) into g-C₃N₄ nanosheets (HF-CNS). The HO⁻ groups are primarily located at the terminal amino groups of the heptazine rings in HF-CNS, while the F⁻ groups are likely incorporated into the g-C₃N₄ lattice by forming C–F bonds. The UV-vis absorption spectra and DFT calculations showed that the electronic band structure, and hence charge carrier recombination, can be tuned by varying the HF amount during the exfoliation process. BET-specific surface area was increased from 18.65 m² g⁻¹ for BCN to 159.87 m² g⁻¹ for HF-CNS. The transient photocurrent increased from 5 μA to 20 μA. HF-CNS significantly improved the photocatalytic degradation of tetracycline, achieving 99% removal in 50 minutes, compared to 20% for BCN. Tetracycline degradation followed pseudo-first-order kinetics, with apparent rate constants (<em>K</em>) increasing from 0.0028 min⁻¹ for BCN to 0.0793 min⁻¹ for HF-CNS, a 30-fold enhancement. The photocatalytic hydrogen evolution for HF-CNS was 11 times higher than that of BCN. The HF-CNS exhibited remarkable stability and reusability, indicating its potential as a promising photocatalyst for green hydrogen production and degradation of organic pollutants.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6833-6844"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694690","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":"Selectively controlled synthesis of diethyl carbonate and methyl ethyl carbonate via transesterification of dimethyl carbonate over a KATriz/Al2O3 catalyst†","authors":"Peixue Wang ,&nbsp;Shimin Liu ,&nbsp;Xinjiang Cui ,&nbsp;Feng Shi","doi":"10.1039/d4cy00979g","DOIUrl":"10.1039/d4cy00979g","url":null,"abstract":"<div><div>In this work, a series of Al₂O₃-supported KATriz (3-amino-1,2,4-triazole potassium) catalysts were developed and employed for the transesterification of dimethyl carbonate (DMC) with ethanol to synthesize diethyl carbonate (DEC) and methyl ethyl carbonate (EMC). It turned out that the 14 wt% KATriz/Al₂O₃ catalyst displayed high activity and possessed adjustability for selective conversion to DEC or EMC <em>via</em> varying the molar ratio of ethanol to DMC. Under optimized conditions, the selectivity of DEC reached 91% when the ratio of DMC to ethanol was 1 : 10. Meanwhile, the selectivity of EMC reached up to 99% when the ratio was 4 : 1, and the catalyst remained stable after a time on stream of 500 h. The prepared catalysts were characterized by BET, TG, XRD, IR, XPS and TPD to establish the relationship between structure and performance. XPS results indicated a significant interaction between KATriz and Al₂O₃, and TPD results showed that 14 wt% KATriz/Al₂O₃ with more accessible basic sites were beneficial for excellent catalytic performance.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6947-6955"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00979g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694692","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":"Synergistic effect of Pd/CZO catalysts and an electric field on complete combustion of lean and humid methane at low temperatures†","authors":"Kei Sugiura ,&nbsp;Takuma Higo ,&nbsp;Nobuki Matsumoto ,&nbsp;Harunobu Tedzuka ,&nbsp;Yasushi Sekine","doi":"10.1039/d4cy00699b","DOIUrl":"10.1039/d4cy00699b","url":null,"abstract":"<div><div>The elimination of unburned methane produced by internal combustion engines is extremely important because of the strong greenhouse effect of methane. Difficulties in controlling unburned methane arise from its characteristics, such as its difficulty of adsorption, low exhaust gas temperatures in an efficient engine, low concentrations of unburned emitted methane, and the coexistence of steam and residual oxygen as coexisting substances in the exit gas. Results of the present study demonstrate that the removal activity of methane by complete combustion was improved dramatically at low temperatures by the application of a DC electric field to the Pd/Ce_<em>x</em>Zr_{1−<em>x</em>}O₂ catalyst system, even under a humid atmosphere. Specifically, 1 wt% Pd/Ce_0.25Zr_0.75O₂ showed very higher methane conversion under humid conditions than under dry conditions at 473 K in the presence of an electric field. To elucidate the reaction mechanisms involved in this process of steam adsorption, we conducted partial pressure dependence tests and activity tests with steam under an electric field.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6775-6781"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00699b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205467","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":"Highly porous boron nitride as a metal-free heterogeneous catalyst for cycloaddition of CO2 to epoxides†","authors":"Teppei Miyamoto ,&nbsp;Atsushi Takagaki ,&nbsp;Jun Tae Song ,&nbsp;Motonori Watanabe ,&nbsp;Tatsumi Ishihara","doi":"10.1039/d4cy01080a","DOIUrl":"10.1039/d4cy01080a","url":null,"abstract":"<div><div>Boron nitride has received much attention as an emerging heterogeneous catalyst. Porous boron nitride catalysts were synthesized using boric acid (B) and urea (U) at different molar ratios <em>via</em> a pyrolysis method and applied for cycloaddition of CO₂ to epoxides as metal-free catalysts. The synthesized boron nitride samples had a turbostratic structure, and their porous properties, such as surface area, pore size distribution, and pore volume, largely depended on the molar ratio of B : U precursors. The sample synthesized at a molar ratio of B : U = 1 : 5 with the highest pore volumes among the samples prepared from boric acid and urea exhibited the highest activity for cycloaddition of CO₂ to epoxides, epichlorohydrin and styrene oxide in the presence of tetrabutylammonium bromide (TBAB). There was a good correlation between the corresponding carbonate yield and the pore properties of the catalyst. The addition of melamine (M) during the synthesis greatly developed the porous structure, exceeding 1000 m² g⁻¹ surface area. The sample synthesized at a molar ratio of B : M : U = 1 : 1 : 5 having a large surface area of 1380 m² g⁻¹ with a high pore volume of 1.8 mL g⁻¹ afforded a remarkable yield of 96% for the reaction of epichlorohydrin. The catalyst could be reused at least three times without a significant loss of activity. A cooperative reaction mechanism was proposed in which the hydroxyl groups of porous boron nitride catalysts as weak Brønsted acid sites polarize the oxygen atom of the epoxide, and the bromide ions of TBAB as Lewis base sites activate the carbon atom of the epoxide by the nucleophilic attack.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6782-6789"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694685","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":"Tuneable, in situ-generated nickel-hydride alkene isomerisation catalyst†","authors":"Melanie A. Kascoutas ,&nbsp;Alison Sy-min Chang ,&nbsp;Kiana E. Kawamura ,&nbsp;Gabriela M. Bailey ,&nbsp;Parker T. Morris ,&nbsp;Elizabeth A. Borst ,&nbsp;Lilliana H. Granados ,&nbsp;Amanda K. Cook","doi":"10.1039/d4cy00974f","DOIUrl":"10.1039/d4cy00974f","url":null,"abstract":"<div><div>A modular, operationally practical Ni(0)/silane alkene isomerisation system has been developed with air-tolerant reagents. An attractive feature of this method is the ability to rapidly screen a variety of N-heterocyclic carbene (NHC) ligands, enabling optimisation through ancillary ligand backbone modification for enhanced reactivity. This system is readily scalable (&gt;1 g alkene) and tolerates a diverse array of functional groups in high <em>E</em>-selectivity, including aryl bromides, heterocycles, tertiary amines, and α,β-unsaturated amides. Preliminary mechanistic experiments support a Ni–H insertion/elimination pathway.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6808-6813"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694687","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":"Ultrasmall RuO2/CoFe2O4 nanoparticles with robust interfacial interactions for the enhanced acidic oxygen evolution reaction†","authors":"Ming Wei ,&nbsp;Liuhua Mu ,&nbsp;Zhiwei Liu ,&nbsp;Feng Gao ,&nbsp;Guangjian Song ,&nbsp;Qiankang Si ,&nbsp;Mao Zhang ,&nbsp;Fangfang Dai ,&nbsp;Min Zhang ,&nbsp;Rui Ding ,&nbsp;Li Yang ,&nbsp;Zhonggui Gao ,&nbsp;Sanzhao Song","doi":"10.1039/d4cy00719k","DOIUrl":"10.1039/d4cy00719k","url":null,"abstract":"<div><div>The acidic stability of RuO₂-based electrocatalysts remains a critical hurdle for proton exchange membrane electrolyzers due to ruthenium leaching. Here, we report an ultrasmall RuO₂/CoFe₂O₄ (RFC) catalyst with robust interfacial interactions, synthesized <em>via</em> an adsorption–pyrolysis method. The RFC catalyst demonstrates an exceptionally low overpotential of 191 mV and outstanding stability, retaining its performance for over 100 hours in 0.5 M H₂SO₄. Experimental analyses indicate that the robust interfacial interactions between RuO₂ and CoFe₂O₄ facilitate efficient charge transfer, significantly enhancing the performance of the oxygen evolution reaction (OER). After the stability test, XRD, Raman, and TEM characterization confirmed that the RFC catalyst maintains its crystal structure and morphology, indicating excellent durability. These findings highlight the potential of RFC catalysts for sustainable hydrogen production and provide a novel approach to the design of advanced electrocatalysts through strategic interfacial engineering, paving the way for improved stability and performance in acidic OER applications.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6824-6832"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00719k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694689","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":"Graphdiyne (CnH2n−2) based copper(i) bromide dual S-scheme heterojunction with AX2O8 type compounds induced electron directional migration","authors":"Xinwan Zhao ,&nbsp;Minjun Lei ,&nbsp;Guangbo Liu ,&nbsp;Zhiliang Jin ,&nbsp;Noritatsu Tsubaki","doi":"10.1039/d4cy01031k","DOIUrl":"10.1039/d4cy01031k","url":null,"abstract":"<div><div>A fundamental strategy for enhancing the performance of photocatalytic water-splitting catalysts is to facilitate the efficient migration of photogenerated charge carriers to establish a heterojunction. In this study, we replace copper foil with CuBr as the catalytic substrate to synthesize a CuBr/graphdiyne composite that exhibits improved hydrogen evolution performance and construct a ZrMo₂O₈/CuBr/graphdiyne dual S-scheme heterojunction in conjunction with AX₂O₈-type compounds. Demonstrated <em>via in situ</em> XPS, charge separation in ZrMo₂O₈, graphdiyne and CuBr can be augmented by constructing dual S-scheme heterojunction to enhance the photocatalytic hydrogen evolution capability. The band structure is confirmed using ultraviolet-visible (UV-vis) spectroscopy and density functional theory (DFT) calculations. Experimental results indicate that the hydrogen evolution rate of the ZrMo₂O₈/CuBr/graphdiyne composite catalyst is five times greater than that of ZrMo₂O₈ alone, three times greater than that of CuBr, and 20 times greater than that of graphdiyne. This work investigates and expands potential synthesis methods for graphdiyne materials within photocatalysis while elucidating mechanisms promoting efficient charge separation. Furthermore, it provides novel perspectives and strategies for enhancing the hydrogen evolution efficiency of ternary photocatalysts through the development of S-scheme heterojunctions.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6854-6868"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694693","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":"Mechanistic differences between the Ru(ii) and Zn(ii)-catalyzed cross-coupling of cyclopropenes with diazo compounds: a DFT study†","authors":"Tiantian Liu ,&nbsp;Kang Lv ,&nbsp;Xiaoguang Bao","doi":"10.1039/d4cy00995a","DOIUrl":"10.1039/d4cy00995a","url":null,"abstract":"<div><div>Transition-metal-catalyzed cross-coupling of two different carbene precursors has been established to construct olefins. In this context, Ru(<span>ii</span>) and Zn(<span>ii</span>)-catalyzed cross-coupling of cyclopropenes with diazo compounds to synthesize 1,3-butadiene derivatives has been developed. Herein, a detailed computational study was performed to shed light on the mechanistic differences between the Ru(<span>ii</span>) and Zn(<span>ii</span>)-catalyzed cross-coupling of cyclopropenes with diazo compounds. For the Ru(<span>ii</span>)-catalyzed reaction, the formation of an Ru–carbene intermediate with diazo compounds is more feasible. Next, cyclopropenes could undergo a [2 + 2] cycloaddition with the Ru–carbene intermediate to form a four-membered ring intermediate, from which an olefin metathesis mechanistic pathway is suggested. Afterward, an unusual alkenyl 1,2-migration might occur to afford the desired cross-coupling product. Meanwhile, for the Zn(<span>ii</span>)-catalyzed reaction, the formation of Zn–carbenoid with cyclopropenes more readily occurs. Then, the nucleophilic C-attack of diazo compounds to the carbene moiety is suggested, leading to the desired product in a concerted manner. The origin of the different chemoselectivities in activating cyclopropenes/diazo compound carbene precursors for the Ru(<span>ii</span>) and Zn(<span>ii</span>) catalysis was discussed.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6917-6923"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694698","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":"Engineering galactose oxidase for efficient cascade synthesis of l-guluronic acid from d-glucose†","authors":"Qingxiu Wang ,&nbsp;Weisong Liu ,&nbsp;Lijing Chang ,&nbsp;Kuncheng Zhang ,&nbsp;Yanbing Shen ,&nbsp;Lingling Zhang","doi":"10.1039/d4cy00697f","DOIUrl":"10.1039/d4cy00697f","url":null,"abstract":"<div><div> <span>l</span>-Guluronic acid, a patented drug with immunomodulatory and anti-inflammatory properties, is traditionally sourced from natural seaweed species or synthesized chemically. Both methods suffer from low selectivity and environmental concerns and there is a high demand to develop a green and efficient approach for <span>l</span>-guluronic acid production. Herein, we successfully developed a two-step enzymatic route to synthesize <span>l</span>-guluronic acid from <span>d</span>-glucose using two oxidases, glucose oxidase (GOx) and galactose oxidase (GOase). Due to the sluggish kinetics of GOase in catalyzing the oxidation of <span>d</span>-gluconic acid, rational design was implemented. Through molecular docking and site saturation mutagenesis, a variant, GOase V3 (T406R/K330R/Y329F), was obtained. The variant exhibited a remarkable 13-fold higher oxidation activity towards <span>d</span>-gluconic acid, reaching 7.8 U mg⁻¹. The substitutions synergistically switch the <span>d</span>-gluconic acid molecule to a favorable conformation and facilitate the specific activation of the primary alcohol group at the C-6 position. In a cascade reaction, the complete conversion of 40 mM <span>d</span>-glucose to <span>l</span>-guluronic acid was achieved in 2 h with 100% selectivity, presenting a promising and green bio-manufacturing strategy for the scalable production of <span>l</span>-guluronic acid.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6956-6967"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694701","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":"Hydrogenation of sulfoxides to sulfides mediated by incomplete cubane-type Mo3S4 clusters: synthetic applications and mechanistic insights†‡","authors":"Juanjo Mateu-Campos ,&nbsp;María Gutiérrez-Blanco ,&nbsp;Eva Guillamón ,&nbsp;Vicent S. Safont ,&nbsp;Rosa Llusar","doi":"10.1039/d4cy00987h","DOIUrl":"10.1039/d4cy00987h","url":null,"abstract":"<div><div>Homogeneous catalysts for the deoxygenation of sulfoxides to sulfides have not been widely explored. Herein, we report a green and efficient protocol for the catalytic hydrogenation of sulfoxides using an air-stable diamino Mo₃S₄ cluster complex under mild conditions (6 bar of H₂ pressure and 50 °C in acetonitrile). Our strategy exhibits excellent group tolerance so it can be widely applied in the late-stage functionalization of pharmacological drugs and other valuable products containing sulfide moieties. Kinetic studies in combination with control experiments and DFT calculations support the operation of a sulfur-based cluster catalysis mechanism similar to the one previously reported for the hydrogenation of azobenzene and semihydrogenation of alkynes. What differentiates this mechanism from the analogous previous ones is that after hydrogen activation at two of the bridging sulfides to form an hydrosulfide intermediate, hydrogen is transferred sequentially first as a proton and then as a hydride.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6845-6853"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694691","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}