Catalysis Science & Technology最新文献

{"title":"Construction of mordenite catalysts with superacid sites for enhanced dimethyl ether carbonylation†","authors":"Yunduo Liu ,&nbsp;Ji Qi ,&nbsp;Kongying Zhu ,&nbsp;Hu Liu ,&nbsp;Xuhong Liu ,&nbsp;Minxing Wang ,&nbsp;Mei-Yan Wang ,&nbsp;Jing Lv ,&nbsp;Shouying Huang ,&nbsp;Xinbin Ma","doi":"10.1039/d5cy00068h","DOIUrl":"10.1039/d5cy00068h","url":null,"abstract":"<div><div>Dimethyl ether (DME) carbonylation to methyl acetate (MA) is a key intermediate step in ethanol synthesis. H-form mordenite (HMOR) efficiently catalyzes this reaction, with Brønsted acid sites (BASs) serving as the active sites. The catalytic performance strongly depends on the strength of BASs. Modification of zeolites with extraframework species is a common method to tune acid strength, among which three-coordinated Al can generate superacid sites by synergistically interacting with Brønsted acid sites. In this study, we employed an ion-exchange method to introduce three-coordinated Al in MOR and systematically investigated their effect on DME carbonylation. ³¹P MAS NMR spectra confirmed that the interaction between three-coordinated Al and BASs led to the formation of superacidic sites. Reactivity results showed that although the total number of BASs decreased after the introduction of three-coordinated Al, the catalytic performance improved significantly, with a 40% increase in the space–time yield of methyl acetate (STY_MA). Mechanistic studies further revealed that these superacidic BASs facilitate the DME dissociation step, accounting for the enhanced activity. These findings provide a systematic strategy for effectively regulating BAS strength in zeolites and offer valuable insights into the rational design and optimization of zeolite catalysts for important industrialized processes.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2510-2518"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826504","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":"Hydride-species-induced enhancement of CO2 hydrogenation selectivity on Ru-atom-modified CeO2 catalysts†","authors":"Qi-feng Zhang ,&nbsp;Ze-Kai Yu ,&nbsp;Zhi-Qiang Wang ,&nbsp;Li Wang ,&nbsp;Xue-Qing Gong ,&nbsp;Yun Guo","doi":"10.1039/d4cy01307g","DOIUrl":"10.1039/d4cy01307g","url":null,"abstract":"<div><div>Controlling product selectivity in heterogeneous catalytic reactions remains challenging, and elucidating the catalyst structure is essential for modulating the reaction selectivity. In this work, mono- and diatomic catalysts with various Ru geometries were tuned to achieve selective hydrogenation of CO₂ to CH₄ or CO. Experimental (such as <em>in situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT)) results show that heterolytic H₂ dissociation occurs at the O–O_v sites on the Ru1/CeO₂ surface to produce hydride (H⁻) species; the resulting H⁻ species promote the selectivity of the CO₂ hydrogenation to form CH₄ at the Ru site <em>via</em> the formation of HCOO* intermediates. In contrast, homolytic H₂ dissociation to produce two Ru–H species on the Ru2/CeO₂ surface facilitates the selective hydrogenation of CO₂ to form COOH* intermediates, which generate CO. This work not only deepens understanding of the mechanism of CO₂ hydrogenation but also provides a novel strategy for developing Ce-based catalysts with high selectivity for CO₂ hydrogenation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2564-2570"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826517","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":"Electrooxidation of ethylene glycol coupled with hydrogen production on porous NiO/Ni@NF nanosheet electrocatalysts†","authors":"Saba A. Aladeemy ,&nbsp;Toleen Rayid AlRijraji ,&nbsp;Mabrook S. Amer ,&nbsp;Prabhakarn Arunachalam ,&nbsp;Abdullah M. Al-Mayouf","doi":"10.1039/d4cy01450b","DOIUrl":"10.1039/d4cy01450b","url":null,"abstract":"<div><div>Electrooxidation of small organic compounds plays a crucial role in clean and efficient energy. This technology has the potential to transform waste materials into useful fuels and chemicals for renewable energy applications. Recently, ethylene glycol (EG) has gained considerable attention due to its high energy density, making it a great fuel for direct alcohol fuel cells. EG electrooxidation has attracted significant interest as an alternative hydrogen energy source to water splitting due to its sustainability and cost effectiveness. In this study, porous NiO/Ni_<em>x</em>@NF nanostructured catalysts were synthesized to enhance alkaline EG electrooxidation reactions. Electrodeposition was employed to grow these NiO/Ni_<em>x</em> structures on nickel foam (NF). The electrochemical characterization results indicate that the porous NiO/Ni_<em>x</em>@NF catalyst exhibits an onset potential of 1.3 V <em>vs.</em> RHE for the electrochemical oxidation of EG in a 1.0 M KOH solution. Additionally, this electrocatalyst has a maximum electrocatalytic activity of 121.6 mA cm⁻², 4.5 times greater than that of the bare Ni@NF catalyst (27.2 mA cm⁻²). Moreover, Ni/NiO@NF demonstrated excellent electrocatalytic performance for both cathodic and anodic reactions, including EG electrooxidation and hydrogen evolution reaction (HER). The developed NiO/Ni_<em>x</em>@NF materials catalyzed EG electrolysis with a faradaic efficiency of 45.5%, demonstrating their ability to facilitate electrolysis. The electrocatalytic activity of NiO/Ni_<em>x</em>@NF porous catalyst toward EG is adequate and stable. Therefore, it appears to be a promising option for using EG in fuel cells.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2571-2583"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826518","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":"Enhanced oxidative coupling of methane over Mn2O3–Na2WO4/TS-1 catalysts by the Ti induced synergistic effect between Mn2O3 and Na2WO4","authors":"Xin Gao ,&nbsp;Jiaxin Song ,&nbsp;Xiaoqiang Fan ,&nbsp;Xuehua Yu ,&nbsp;Lian Kong ,&nbsp;Xia Xiao ,&nbsp;Zean Xie ,&nbsp;Zhen Zhao","doi":"10.1039/d5cy00097a","DOIUrl":"10.1039/d5cy00097a","url":null,"abstract":"<div><div>Oxidative coupling of methane (OCM) can directly convert natural gas into C₂ hydrocarbons (C₂H₄ and C₂H₆). The Mn₂O₃–Na₂WO₄/SiO₂ catalyst, owing to its high OCM performance and thermostability at high temperatures, has become a promising OCM catalyst. The synergy and dispersion of Na₂WO₄ and Mn₂O₃ are important factors in improving OCM performance, and the selection of the support has a significant impact on their dispersion and interaction. To enhance the synergistic effect and dispersion of Na₂WO₄ and Mn₂O₃, a TS-1 support doped with varying amounts of Ti was selected for the Mn₂O₃–Na₂WO₄/<em>x</em>TS-1 (Na–W–Mn/<em>x</em>TS-1) catalyst preparation. The characterization results showed that Ti addition promoted Na₂WO₄ dispersion and enhanced interactions between Na₂WO₄ and Mn₂O₃. Moreover, Ti doping effectively promoted the generation of active oxygen species and increased the conversion of methane, thereby increasing the C₂ yield. The Na–W–Mn/8%TS-1 catalyst exhibited the highest OCM performance, with a 20.0% C₂ yield and 46.8% CH₄ conversion. The enhanced OCM performance may be caused by the increased dispersion of Na₂WO₄ and Mn₂O₃ induced by the atomic-level Ti doping in the TS-1 support, which promoted their interaction and increased the number of lattice oxygen species.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2628-2641"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826523","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":"3d-metal based anodic pincer electro-catalysts dispersed in solution for the electro-catalytic oxidation of (m)ethanol†","authors":"Niharika Tanwar ,&nbsp;Pran Gobinda Nandi ,&nbsp;Sunil Dhole ,&nbsp;Raksh Vir Jasra ,&nbsp;Akshai Kumar","doi":"10.1039/d4cy01496k","DOIUrl":"10.1039/d4cy01496k","url":null,"abstract":"<div><div>Using banana-leaf extract as the reducing agent, a green protocol has been formulated for the synthesis of Ni/Co/Cr based metal oxide/hydroxide nanoparticles starting either from their metal salt precursors or from their bis(iminopyridine) pincer complexes. Thorough characterization has been performed using powder-XRD, FESEM, FETEM, XPS, MALDI and FT-IR analysis to infer the phase, morphology, size and chemical composition of these heterogeneous particles. The nano-particles (NPs) derived from (^iPr2NNN)CoCl₂ containing CoO₂ and Co₃O₄ mixed phase oxides possessing a spherical morphology turned out to be superior among the 12 nano-catalysts that were screened. While a current density of 24.90 ± 10.74 mA cm⁻² and 260.06 ± 3.06 mA cm⁻² was obtained for methanol electro-oxidation (MOR), a current density of 33.39 ± 1.28 mA cm⁻² and 235.03 ± 4.03 mA cm⁻² was observed during ethanol electro-oxidation (EOR) at room temperature in NaOH as the supporting electrolyte using a carbon based electrode assembly. At 60 °C, the current densities in the (^iPr2NNN)CoCl₂ NP catalyzed MOR increased up to 222.23 mA cm⁻² and 451.32 mA cm⁻² at a lower potential of 0.69 V and 1.22 V <em>vs.</em> Ag/AgCl. The electro-oxidation is majorly complete with zero evolution of CO₂ as it gets trapped by the supporting electrolyte as a value-added chemical Na₂CO₃. For the MOR and EOR, up to 98% and 82% respectively of Na₂CO₃ were obtained after 12 hours of controlled potential electrolysis. The (^iPr2NNN)CoCl₂ NPs were also found to be highly stable and fairly active with a current retention of 78.60% and 64.0% for MOR and EOR respectively. The catalytic activity and the yield of Na₂CO₃ obtained with the top-three best of the considered catalysts had a linear correlation with the electrochemical active surface area (ECSA), CA stability and current retention along with the diffusion coefficient while following the trend (^iPr2NNN)CoCl₂ NPs &gt; (^Ph2NNN)NiCl₂(CH₃CN) NPs &gt; (^Ph2NNN)CrCl₃ NPs. In this work, a unique approach of suspending the electro-catalysts in solution rather than using them on bulk electrodes has been executed to probe their electro-catalytic activity towards (m)ethanol which not only leads to high current densities but also generates industrially valuable Na₂CO₃.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2493-2509"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826503","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":"Atomic-scale secondary electron imaging for heterogeneous catalysis research","authors":"Sooyeon Hwang ,&nbsp;Judith C. Yang","doi":"10.1039/d4cy01551g","DOIUrl":"10.1039/d4cy01551g","url":null,"abstract":"<div><div>Surface characterization at the atomic scale is essential for understanding the catalytic properties of supported metal nanoparticles. Secondary electron (SE) imaging in scanning transmission electron microscopy (STEM) provides three-dimensional surface topographic information, enabling the characterization of the size, morphology, and distribution of supported nanoparticles. Furthermore, real-time observation of catalyst materials in a gaseous environment would enhance the understanding of catalyst dynamics under operational conditions. Ongoing technical developments in SE-STEM and advancements in computational methods are expected to facilitate atomic-scale surface observations and enable more quantitative and statistical analyses. This progress will not only elucidate fundamental mechanisms at the atomic level but also provide comprehensive and universal insights into catalyst performances. This minireview showcases the recent advancements and research findings in surface-sensitive SE imaging in STEM for the characterization of active catalyst materials.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2450-2458"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826497","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":"Automation accelerated screening of H-bond-rich iridium photosensitisers for hydrogen generation†","authors":"T. Harri Jones ,&nbsp;Christopher F. Bradshaw ,&nbsp;John W. Ward ,&nbsp;Barry A. Blight","doi":"10.1039/d5cy00176e","DOIUrl":"10.1039/d5cy00176e","url":null,"abstract":"<div><div>In the pursuit of a stable hydrogen evolution photosensitiser, we demonstrate the incorporation of a series of our H-bond rich guanidine-styled iridium(<span>iii</span>) complexes into a catalytic system. Using automation accelerated catalysis screening techniques we optimised our system quickly and effectively to observe how these strongly H-bonding complexes may perform. Proven to be photo-electronically suitable, and with effective electron transfer abilities evidenced by Stern–Volmer mechanistic studies, the complexes showed modest levels of H₂ evolution in comparison to previously investigated photosensitisers with general formula [Ir(C^N)₂(N^N)].</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2459-2465"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826498","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":"Adsorbed O promotes alternative, nonselective oxametallacycle reaction pathways in Ag-catalyzed epoxidation†","authors":"Shengjie Zhang ,&nbsp;Sarah M. Stratton ,&nbsp;Matthew M. Montemore","doi":"10.1039/d4cy01486c","DOIUrl":"10.1039/d4cy01486c","url":null,"abstract":"<div><div>Ethylene oxide (EO) is a vital compound used as an intermediate in the production of other important compounds, such as ethylene glycol and glycol ether. EO is produced by selective ethylene oxidation (epoxidation) over supported Ag catalysts. Achieving high selectivity is the primary goal of research in this area, and understanding the factors that influence selectivity is thus critical for improving performance. The most widely accepted intermediate in EO production is the oxametallacycle (OMC). However, possible reactions between surface O and the OMC have not been comprehensively studied. In this work, density functional theory was used to systematically study the possible reaction pathways from the OMC in the presence of surface O. We find that surface O opens up two kinetically and thermodynamically favorable pathways that have received little or no attention in previous studies, neither of which form EO. Specifically, O-assisted C–H bond scission and the formation of ethylenedioxy are quite facile and predicted to be more favorable than the traditional EO (ring-closure) and acetaldehyde (H transfer) pathways. Thus, the predicted selectivity in the presence of coadsorbed O is very low, less than 0.1% at typical reaction temperatures. Furthermore, surface O has a similar effect on the propylene-derived OMC, which may have relevance to propylene oxidation. These results show the potential importance of surface O in influencing selectivity, as surface O greatly promotes these non-selective reactions and should therefore be minimized. These O-promoted reaction pathways should be considered in both design and kinetic modelling of EO catalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2551-2557"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826515","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":"Near-infrared light-triggered NaYF4: Yb3+, Tm3+@ZnO@RGO@Ag photocatalyst for efficient degradation of tetracycline†","authors":"Yuangong Ma ,&nbsp;Youlin Huang ,&nbsp;Wensheng Zhang ,&nbsp;Zhishan Liang ,&nbsp;Bo Ding ,&nbsp;Dongfang Han ,&nbsp;Dongxue Han ,&nbsp;Li Niu","doi":"10.1039/d5cy00049a","DOIUrl":"10.1039/d5cy00049a","url":null,"abstract":"<div><div>In the domain of photocatalysis, harnessing solar energy, particularly the near-infrared (NIR) spectrum, presents formidable challenges. To overcome these, a novel NIR-responsive photocatalyst, denoted as NYT@ZnO@RGO@Ag, was meticulously crafted. This photocatalyst comprises a NaYF₄: Yb³⁺, Tm³⁺@ZnO structure supported on reduced graphene oxide (RGO) and further composited with silver nanoparticles. It was rigorously evaluated for its performance in photodegrading tetracycline (TC) antibiotics as a model compound. Leveraging the unique properties of upconversion materials, wide bandgap semiconductors, and localized surface plasmon resonance (LSPR), the NYT@ZnO@RGO@Ag catalyst exhibited an impressive photodegradation rate of 93.6% for TC under NIR light exposure. This efficiency surpassed that of NYT@ZnO (38.2%) and NYT@ZnO@RGO (72.3%). The remarkable enhancement in NIR-driven photocatalysis observed in NYT@ZnO@RGO@Ag is primarily attributed to the efficient process of fluorescence resonance energy transfer (FRET) from NYT to its each component. This process enhances photo-induced carrier generation and facilitates efficient transfer and energy utilization under NIR irradiation. The present study offers a promising approach for NIR-driven photocatalytic degradation of pollutants in environments with limited light exposure or even under dark conditions.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2595-2605"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826520","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":"A review of reversible hydrogenation and dehydrogenation catalysts for liquid organic hydrogen carriers","authors":"Meiying Dai ,&nbsp;Yibo Qin ,&nbsp;Longfei Chen ,&nbsp;Xinqing Chen","doi":"10.1039/d4cy01483a","DOIUrl":"10.1039/d4cy01483a","url":null,"abstract":"<div><div>Hydrogen energy is widely regarded as a green, low-carbon, and efficient secondary energy source with immense potential for future energy systems. As a clean alternative to the traditional fuels, its use could significantly reduce carbon emissions and contribute to a more sustainable energy landscape. However, one of the key challenges in realizing this potential is the safe and efficient storage of hydrogen. Among the various storage technologies, liquid organic hydrogen carriers (LOHCs) have emerged as a promising solution for both on-board and off-board hydrogen storage systems. LOHCs offer notable advantages, including low cost, high hydrogen storage capacity, and storage efficiency. Despite these benefits, LOHC technology faces several obstacles, such as high reaction temperatures, reliance on expensive noble metal catalysts, and the relatively low efficiency of non-precious metal catalysts during hydrogenation and dehydrogenation processes. Consequently, there has been growing interest in developing more efficient and cost-effective catalysts to overcome these limitations. This paper reviews the recent advancements in the catalytic hydrogenation and dehydrogenation of LOHCs, particularly focusing on the role of metal catalysts in enhancing the reversible hydrogenation and release of hydrogen. The insights provided are intended to guide the rational design of next-generation catalysts, which could significantly enhance the performance of hydrogen storage systems and advance hydrogen technology toward broader practical applications.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 8","pages":"Pages 2440-2449"},"PeriodicalIF":4.4,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826496","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}