Catalysis Science & Technology最新文献

{"title":"Machine learning and text mining approaches to design selective catalyst reduction synthesis routes†","authors":"Shuyuan Li ,&nbsp;Chenyu Huang ,&nbsp;Yunjiang Zhang ,&nbsp;Jing Li ,&nbsp;Shaorui Sun","doi":"10.1039/d4cy01159g","DOIUrl":"10.1039/d4cy01159g","url":null,"abstract":"<div><div>The development of selective catalytic reduction (SCR) catalysts is often hindered by the complexity of experimental processes and the time-consuming trial-and-error approaches. Machine learning offers a promising solution by enabling more efficient and data-driven catalyst design. In this study, information was automatically extracted from the SCR-related scientific literature, including catalyst synthesis and catalyst properties, using rule-based techniques. These extracted data were then structured through feature engineering to build a machine learning-ready dataset. Models such as extreme gradient boosting regression (XGBR) and random forest (RF) were employed to predict catalyst performance and identify key factors influencing selectivity and conversion rates. To optimize synthesis routes, the designed synthesizable space was combined with the machine learning models to optimize key parameters and predict synthesis routes for SCR catalysts. Finally, synthesis information for SCR catalysts with high-performance was recommended. This work demonstrates the potential of using machine learning to accelerate SCR catalyst development, providing a scalable method for designing more efficient catalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1217-1227"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430664","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":"Oxime-palladacycle complex supported on magnetic nanoparticles: a recyclable catalyst for Suzuki-type decarbonylative cross-coupling of esters with aryl boronic acid†","authors":"Tahshina Begum ,&nbsp;Sazida Yasmin Sultana ,&nbsp;Hasmita Hasin Mou ,&nbsp;Nashreen S. Islam","doi":"10.1039/d4cy01470g","DOIUrl":"10.1039/d4cy01470g","url":null,"abstract":"<div><div>To simplify the reuse and recovery of catalysts, we have developed a magnetically separable, oxime-based palladacycle complex (Fe₃O₄@TEOS-palladacycle) and demonstrated that it is a very efficient and versatile catalyst for Suzuki-type decarbonylative cross-coupling of esters with aryl boronic acid in 2-MeTHF under refluxing conditions. The novel catalyst was synthesized using a multi-step process involving surface modification, oxime-functionalization, and palladium immobilization, and characterized by FT-IR, P-XRD, FE-SEM, TEM, EDX, TGA, VSM, XPS, and ICP-OES analysis. This protocol is advantageous due to the utilization of non-toxic, biomass-derived 2-MeTHF as a green solvent medium. The Fe₃O₄@TEOS-palladacycle was also used as an efficient catalyst for the preparation of boscalid, a significant fungicide, <em>via</em> a decarbonylative approach. Moreover, the solid catalyst could be recovered easily by a simple magnetic separation technique and reused five times without significant loss of its catalytic activity with negligible metal leaching. More importantly, the wide range of functional groups found to be compatible with the given reaction conditions are the main merits of this protocol.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1247-1258"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430665","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":"Investigating silicatein selectivity and specificity in silicon–oxygen bond condensation and metathesis†","authors":"Chisom S. Egedeuzu ,&nbsp;Peter G. Taylor ,&nbsp;Lu Shin Wong","doi":"10.1039/d4cy00985a","DOIUrl":"10.1039/d4cy00985a","url":null,"abstract":"<div><div>Silyl ethers are an important group of compounds containing Si–O bonds with a variety of applications, but their formation currently relies on reagents that are undesirable from a sustainability perspective. This study is a further investigation of the biocatalytic silylation of alcohols using silanols or silyl ethers as the silyl donor, with the recombinant enzyme silicatein-α as the catalyst. It was found that the model enzyme-catalysed reactions gave better conversion of phenol to its corresponding phenoxy silane compared to the aliphatic <em>n</em>-octanol. The enzyme was selective for phenols and did not catalyse disiloxane formation. In addition, it was observed that the optimum temperature for the enzymatic conversion was 75 °C. The enzyme also showed superior catalysis compared to conventional small molecule base catalysts such as imidazole and triethylamine.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1009-1015"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy00985a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430622","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":"An examination of dimethyl oxalate hydrogenation to methyl glycolate on silica-supported Ni–Co alloy catalysts†","authors":"Donghui Xiao ,&nbsp;Shilong Xie ,&nbsp;Xin Gao ,&nbsp;Riguang Zhang ,&nbsp;Chun-Ran Chang","doi":"10.1039/d4cy01278j","DOIUrl":"10.1039/d4cy01278j","url":null,"abstract":"<div><div>The selective hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) is becoming increasingly attractive for the industrial production of polyglycolic acid (PGA) biodegradable plastics. However, it is still necessary to develop highly selective/active and affordable DMO hydrogenation catalysts for the large-scale production of MG and PGA. In this report, silica-supported Ni–Co alloy catalysts were meticulously investigated for the selective hydrogenation of dimethyl oxalate to methyl glycolate. Compared with monometallic Ni or Co, the supported Ni–Co alloy catalysts with an appropriate doping of Co in Ni resulted in the significant promotion of dimethyl oxalate conversion and methyl glycolate selectivity at mild temperature (180 °C). Optimized dimethyl oxalate conversion and selectivity for methyl glycolate were 87% and 86%, respectively, on the 15Ni–10Co/SiO₂ catalyst. The promotion of dimethyl oxalate conversion was attributed to the large capacity and strong strength of hydrogen adsorption, as proven <em>via</em> H₂-TPD, and the active sites with uniform strength for CO adsorption and dimethyl oxalate (or key oxygenated intermediates) adsorption, as proven <em>via in situ</em> CO-DRIFTS. These phenomena were enhanced by the effective interaction between Ni and Co. Furthermore, it was found that the strength of acid sites has an influence on product selectivity control for ethanol and methyl formate; particularly, the synergy between the acid sites and metal sites may facilitate deep hydrogenation of dimethyl oxalate to form unexpected methyl formate. This study not only shows the catalytic behavior of dimethyl oxalate hydrogenation on non-precious Ni–Co alloy catalysts but also provides new insights into designing Ni-based catalysts for the selective hydrogenation of oxygenates with multiple ester groups.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1041-1054"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430626","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":"The promoting effect of Nb on Ni/SiO2 in the hydrodeoxygenation of lignin derivatives to cycloalkanes†","authors":"Xiyue Lu ,&nbsp;Hui Wang ,&nbsp;Wei Liu ,&nbsp;Mooeez ur Rehman ,&nbsp;Lu Wang ,&nbsp;Yan Xu ,&nbsp;Shengnian Wang ,&nbsp;Yujun Zhao","doi":"10.1039/d4cy01226g","DOIUrl":"10.1039/d4cy01226g","url":null,"abstract":"<div><div>Effective non-noble metal catalysts are critical for upgrading lignin-derived compounds into valuable products by hydrodeoxygenation (HDO). In this study, new Ni⁰–NiNbO_<em>x</em>/SiO₂ catalysts were synthesized by combining sol–gel and impregnation methods. The HDO performance of these catalysts was then evaluated in the production of cycloalkanes from lignin-derived phenolic compounds. These Ni⁰–NiNbO_<em>x</em>/SiO₂ catalysts present a considerably larger specific surface area than their Ni/SiO₂ counterparts. They work as bifunctional catalysts in the HDO process, where Ni⁰ species act as active sites for hydrogenation while NiNbO_<em>x</em> provides the Lewis acid sites necessary for deoxygenation. In this way, a significant improvement in the cyclohexane yield from 18% to 94.4% in guaiacol HDO was achieved on these Ni⁰–NiNbO_<em>x</em>/SiO₂ catalysts. The best catalyst 10Ni/20Nb@SiO₂ exhibits complete conversion of guaiacol and almost 100% selectivity of cycloalkanes at 250 °C. The apparent activation energy for the 10Ni/20Nb@SiO₂ catalyst was identified to be 54.2 kJ mol⁻¹, notably lower than that for other reported Ni-based catalysts. These findings highlight the superior performance of Ni⁰–NiNbO_<em>x</em>/SiO₂ catalysts in the HDO of lignin-derived phenolic compounds, underscoring their great potential in producing cycloalkanes from renewable resources. Our efforts help pave the way for the catalytic transformation of lignin into valuable biofuels to advance the global mission toward a sustainable supply of fuels.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1134-1148"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430645","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":"Tungsten-dioxo single-site heterogeneous catalyst on carbon: synthesis, structure, and catalysis†","authors":"Amol Agarwal ,&nbsp;Yiqi Liu ,&nbsp;Miyuki Hanazawa ,&nbsp;Jiaqi Li ,&nbsp;Takayuki Nakamuro ,&nbsp;Eiichi Nakamura ,&nbsp;Yosi Kratish ,&nbsp;Tobin J. Marks","doi":"10.1039/d4cy01517g","DOIUrl":"10.1039/d4cy01517g","url":null,"abstract":"<div><div>This study investigates the application of a novel third-row metal, tungsten, to carbon-supported single-site metal-oxo heterogeneous catalysis. Tungsten is a green and earth-abundant metal, but an unexplored candidate in this role. The carbon (AC = activated carbon)-supported tungsten dioxo complex, AC/WO₂ was prepared <em>via</em> grafting of (DME)WO₂Cl₂ (DME = 1,2-dimethoxyethane) onto high-surface-area activated carbon. AC/WO₂ was fully characterized by ICP-OES, XPS, EXAFS, XANES, SMART-EM, and DFT. W 4d_7/2 XPS and W L_III-Edge XANES assign the oxidation state as W(<span>vi</span>), while EXAFS reveals two WO double and two W–O single bonds at distances of 1.73 and 1.92 Å, respectively. These data align well with DFT computational results, supporting the structure as Carbon(–μ-O–)₂M(O)₂. SMART-EM verifies that single W(<span>vi</span>) catalytic sites are bonded in an out-of-plane manner. The catalytic performance of air- and water-stable AC/WO₂ is compared to that of AC/MoO₂. AC/WO₂ is more active and selective than the molybdenum analog in mediating alcohol dehydration of various substrates, and is recyclable. Notably, AC/WO₂ is an effective and recyclable catalyst for primary aliphatic alcohol dehydration and forms no dehydrogenation side products in contrast to AC/MoO₂. However, AC/WO₂ is less effective in epoxidation and PET depolymerization. Overall, this work demonstrates the potential of carbon-supported third row metals for future studies.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1272-1279"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy01517g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430669","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":"Nature of sulfonyl deactivation/activation by metal catalysts†","authors":"Zhihui Li ,&nbsp;Lanbo Liu ,&nbsp;Wan Li ,&nbsp;Xueqing Song ,&nbsp;Zheng Wang ,&nbsp;Longfei Li","doi":"10.1039/d4cy01350f","DOIUrl":"10.1039/d4cy01350f","url":null,"abstract":"<div><div>Molecule activation theories are important in catalytic reactions, but sulfonyl activation remains unclear despite the fact that sulfonyl is a widely used leaving group in chemical synthesis. To unveil the nature of sulfonyl deactivation/activation by metal catalysts, the mechanisms of the competitive metal-catalyzed α-alkylation of sulfones and sulfonyl dissociation (Julia olefination) reactions are comprehensively investigated. A favorable metal-catalyzed mechanism is first proposed for the sulfonyl dissociation reaction. The sulfonyl dissociation and chemoselectivity are revealed to originate from hydride addition into the CC bond of the vinyl sulfone intermediate. Through natural localized molecular orbital analysis, a sulfonyl deactivation model with a π_C(α)C(β) → σ*_S–O hyperconjugation effect and a sulfonyl activation model with π_C(α)C(β) → π*_Ph conjugation effect are proposed. Guided by the sulfonyl activation model, switchable chemoselectivity strategies are provided to control these reactions.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1016-1027"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430623","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":"Higher BTEX aromatic yield from ethanol over desilicated H,Zn-[Al]ZSM-5 catalysts†","authors":"Daniel Dittmann ,&nbsp;Alime Ileri ,&nbsp;Dennis Strassheim ,&nbsp;Michael Dyballa","doi":"10.1039/d4cy01062k","DOIUrl":"10.1039/d4cy01062k","url":null,"abstract":"<div><div>The amount of BTEX aromatics obtained from the conversion of ethanol (ETA) is increased by combining ZSM-5 catalysts having optimum acidity with desilication and zinc ion exchange. Zinc leads to preferred dehydrogenation instead of hydrogen transfer. It decreases the share of paraffin products and increases BTEX contents (up to <em>S</em>_BTEX = 50%) at the cost of lifetime. The latter can be increased <em>via</em> desilication. An ethylene feed increases lifetime and BTEX production as result of oxygenate absence. Combination of improvements resulted in a C₂ conversion capacity of 206 g g⁻¹ and a total yield of BTEX aromatics of 31.6 g g⁻¹, which is about a factor of 2–3 times better than the respective values found for microporous, mesoporous, or microporous Zn-exchanged materials. <em>In situ</em> UV/vis spectra reveal that desilicated samples coke significantly slower than microporous samples, whereas Zn exchange supports the formation of coke. Thus, by a clever combination of suitable post-modifications, a significantly higher BTEX production from the primary source ethanol can be achieved.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1028-1040"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy01062k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430624","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":"Unraveling the synergistic mechanism of multimetals in Ni3Cu–Sn catalysts for selective hydrogenation of phenylacetylene†","authors":"Aohui Xiao ,&nbsp;Kehang Ruan ,&nbsp;Yuqi Zhou ,&nbsp;Hongjie Cui ,&nbsp;Zhiming Zhou","doi":"10.1039/d4cy01464b","DOIUrl":"10.1039/d4cy01464b","url":null,"abstract":"<div><div>The selective hydrogenation of phenylacetylene plays an important role in purifying the styrene monomer. Non-noble Ni₃Cu–Sn trimetallic catalysts have demonstrated high styrene selectivity at an acceptable reaction rate in phenylacetylene hydrogenation. However, the synergistic mechanism of Ni, Cu, and Sn in complex Ni–Cu–Sn alloys remains unclear, restricting the design and development of more efficient trimetallic catalysts. Herein, we explore the interactions among the three metals by employing relatively simple Ni₃Cu_{(1−<em>y</em>)}Sn_<em>y</em> pseudo-binary alloys, based on the similarity in crystal structure between Ni₃CuSn_<em>x</em>/SBA-15 and Ni₃Cu_{(1−<em>y</em>)}Sn_<em>y</em>/SBA-15 catalysts. Density functional theory calculations reveal that Ni and Cu atoms directly contribute to the adsorption of phenylacetylene, styrene and hydrogen at trimer sites, while Sn atoms modulate the electronic and geometric properties of Ni. As the degree of Cu substitution by Sn in cubic Ni₃Cu_{(1−<em>y</em>)}Sn_<em>y</em> planes increases, the Ni–Ni bond lengthens and Ni atoms become more electron-rich, thereby weakening styrene adsorption. Nevertheless, more Sn substitution induces a cubic-to-hexagonal crystal structure transformation, leading to an adverse effect. This trend is supported by experimental results: styrene selectivity on Ni₃Cu_{(1−<em>y</em>)}Sn_<em>y</em>/SBA-15 increases with <em>y</em> up to 0.5, but decreases with further Sn substitution due to the crystal structure transformation. The hydrogenation activity of the catalysts consistently deceases with increasing <em>y</em>, likely owing to a reduction in the concentration of Ni trimers, which serve as the primary adsorption sites for reactants. Therefore, the key to achieving high styrene selectivity is increasing the degree of Cu substitution by Sn in Ni₃Cu–Sn catalysts until the cubic-to-hexagonal transformation occurs.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1203-1216"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430650","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":"Retraction: Photocatalytic activation and utilization of CO2 for N-formylation of amines promoted by a zinc(ii) phthalocyanine grafted on g-carbon nitride hybrid","authors":"Anil Malik, Pankaj Kumar Prajapati, B. Moses Abraham, Sakshi Bhatt, Purashri Basyach and Suman L. Jain","doi":"10.1039/D5CY90006A","DOIUrl":"https://doi.org/10.1039/D5CY90006A","url":null,"abstract":"<p >Retraction of ‘Photocatalytic activation and utilization of CO<small>₂</small> for <em>N</em>-formylation of amines promoted by a zinc(<small>II</small>) phthalocyanine grafted on g-carbon nitride hybrid’ by Anil Malik <em>et al.</em>, <em>Catal. Sci. Technol.</em>, 2022, <strong>12</strong>, 2688–2702, https://doi.org/10.1039/D1CY02286E.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 3","pages":" 947-947"},"PeriodicalIF":4.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d5cy90006a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107434","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}