Catalysis Science & Technology最新文献

{"title":"First-principles investigation of an efficient non-noble single-atom catalyst Fe1/Ti2CO2 for formaldehyde oxidation","authors":"Yongkang Zhang, Yuting Fu, Kaibin Su, Yuhang Wang, Fengping Wang","doi":"10.1039/d4cy00809j","DOIUrl":"https://doi.org/10.1039/d4cy00809j","url":null,"abstract":"Indoor formaldehyde (HCHO) removal holds paramount significance for human health, particularly in mild conditions. Here, we introduce a new non-noble single-atom catalyst, Fe<small>₁</small>/Ti<small>₂</small>CO<small>₂</small>, designed for formaldehyde oxidation. The oxidation mechanism of HCHO on Fe<small>₁</small>/Ti<small>₂</small>CO<small>₂</small> was studied by density functional theory. The HCHO oxidation mechanisms of the Langmuir–Hinshelwood (LH) mechanism and the Eley–Rideal (ER) mechanism were explored. The activation energies of all possible intermediates and their elementary steps in the reaction were given. Through thermodynamic and kinetic analysis, reaction rates at different temperatures ranging from 300 K to 600 K were obtained. In the temperature range studied, the reaction of formaldehyde oxidation can occur spontaneously and irreversibly. The minimum activation energy is only 0.73 eV, and the dissociation of CO<small>₂</small> and H<small>₂</small>O is endothermic, with an energy of 1.30 eV. This indicates promising practical applications for the catalyst. Our work can assist in designing new catalysts for formaldehyde oxidation under mild conditions.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142260053","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":"Recent advances in bifunctional synthesis gas conversion to chemicals and fuels with a comparison to monofunctional processes†","authors":"","doi":"10.1039/d4cy00437j","DOIUrl":"10.1039/d4cy00437j","url":null,"abstract":"<div><p>In order to meet the climate goals of the Paris Agreement and limit the potentially catastrophic consequences of climate change, we must move away from the use of fossil feedstocks for the production of chemicals and fuels. The conversion of synthesis gas (a mixture of hydrogen, carbon monoxide and/or carbon dioxide) can contribute to this. Several reactions allow to convert synthesis gas to oxygenates (such as methanol), olefins or waxes. In a consecutive step, these products can be further converted into chemicals, such as dimethyl ether, short olefins, or aromatics. Alternatively, fuels like gasoline, diesel, or kerosene can be produced. These two different steps can be combined using bifunctional catalysis for direct conversion of synthesis gas to chemicals and fuels. The synergistic effects of combining two different catalysts are discussed in terms of activity and selectivity and compared to processes based on consecutive reaction with single conversion steps. We found that bifunctional catalysis can be a strong tool for the highly selective production of dimethyl ether and gasoline with high octane numbers. In terms of selectivity bifunctional catalysis for short olefins or aromatics struggles to compete with processes consisting of single catalytic conversion steps.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00437j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141785057","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":"Investigating the interplay of hydrogen transfer, protolytic cracking, and dehydrogenation reactions over faujasite zeolites by using isooctane conversion as a probe†","authors":"","doi":"10.1039/d4cy00338a","DOIUrl":"10.1039/d4cy00338a","url":null,"abstract":"<div><p>Isooctane can serve as a useful probe to investigate hydrogen transfer reactions in faujasite zeolites. Its unique nature, containing both quaternary and ternary carbons, allows for appreciable protolytic cracking and hydrogen transfer reaction rates under modest reaction conditions where zeolite structural integrity is preserved. We show how a simple plot of C₄ alkane selectivity <em>vs.</em> C₁ selectivity allows for visible quantification of the tradeoffs between protolytic cracking and hydrogen transfer pathways. Similarly, we illustrate how deviations from a linear relationship between these two products can be used to quantify dehydrogenation rates. The role of metal cations such as Na, Ca, and Co as titrants was explored to modify the rates of these reaction pathways, enabling quantitative assessment of cation titration at not only promoting new pathways, but selectively titrating sites that are most active for protolytic cracking. We further contrast this simple approach in ternary diagrams that visually depict the contributions of catalyst modifications and reaction conditions on the three parallel reactions, revealing that Na selectively titrates sites responsible for protolytic cracking while Co promotes dehydrogenation reactions. The effects of isooctane conversion, reaction time on stream, and isooctane partial pressure on isooctane cracking selectivity are discussed. We have also applied the quantitative analysis derived from the isooctane cracking probe to explain the product distribution of <em>n</em>-heptane cracking, an example of a linear alkane that exhibits a greater variety of products. This comparison demonstrates that the trends observed in isooctane cracking for a series of catalysts are translatable to <em>n</em>-heptane cracking, highlighting the practical application of the isooctane cracking probe to more complex feeds. Finally, we reveal that the incorporation of Lanthanum, often added to Y zeolites in industrial catalytic cracking operations, enhances both hydrogen transfer rates and dehydrogenation rate of alkanes. This comprehensive approach improves our understanding of catalyst performance and reaction mechanisms while offering insight for practical applications.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141872291","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":"Zeolite-based materials eliminating nitrogen oxides (NOx) and volatile organic compounds (VOCs): advances and future perspectives","authors":"","doi":"10.1039/d4cy00841c","DOIUrl":"10.1039/d4cy00841c","url":null,"abstract":"<div><p>As awareness of environmental protection increases, the most inextricably linked issue of greatest concern is atmospheric pollution. In particular, the major gaseous pollutants, such as nitrogen oxides (NO_x) and volatile organic compounds (VOCs), which are the precursors for the formation of fine particulate matter and ozone, have attracted significant attention. To eliminate these pollutants, zeolite-based materials have become the indispensable adsorbents and/or catalysts due to their remarkable shape selectivity, adsorption and ion exchange capability, high hydrothermal durability, tunable acidity and polarity, and affordable production expenses. Furthermore, modifying their porous architectures and compositions, and the incorporation of exotic species could lead to an unprecedented high performance in a wide range of challenging environmental governance processes. In this perspective, we focus on the latest advancements in employing zeolite-based materials to eliminate NO_x and VOCs. Especially, the impacts of porous structures and components on the performance of adsorption and catalytic conversion were elucidated. Finally, the potential challenges and future opportunities for the utilization of zeolite-based materials are identified and outlined to meet the ever-increasing requirements for the improved atmospheric environment in the future.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141936832","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":"Markovnikov selective hydroaminocarbonylation of alkenes over a porous monophoshine polymer supported palladium catalyst†","authors":"","doi":"10.1039/d4cy00742e","DOIUrl":"10.1039/d4cy00742e","url":null,"abstract":"<div><p>Here we develop a porous monophoshine polymer supported Pd catalyst (Pd/POL-<em>m</em>-3vPPh₃) for hydroaminocarbonylation of aromatic alkenes with amines, showing excellent catalytic activity (up to 97% yield) and Markovnikov selectivity (up to 99%) for producing branched amides. This catalyst exhibits broad substrate compatibility, and is reused for two times with no significant decline in the performance and three times with no significant Pd leaching, as well as applied for the synthesis of naproxen.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141936838","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":"Suppressing on-stream deactivation of CuSiO2 catalysts in the dehydrogenation of bioethanol to acetaldehyde†","authors":"","doi":"10.1039/d4cy00646a","DOIUrl":"10.1039/d4cy00646a","url":null,"abstract":"<div><p>Bioethanol upgrading to valuable platform molecules is a cornerstone of the emerging “integrated biorefinery” concept. Although active catalysts have already been developed for the non-oxidative dehydrogenation of ethanol to acetaldehyde, their rapid deactivation – through coking and sintering – is still an unsolved challenge. Herein, we study a 7.4 wt% Cu–SiO₂ catalyst at 573 K for 8 or 24 hours under stable ethanol feed, we report in-depth characterization of the spent catalysts to univocally describe deactivation phenomena, and we propose reaction engineering procedures based on gas co-feed (O₂ or H₂) to decisively enhance the catalyst stability. Under the standard conditions, the pristine catalyst undergoes fast deactivation, as conversion drops from ∼95% to ∼25% in about 8 hours. While sintering is shown to occur during the reaction, we demonstrate that the main cause of deactivation is actually the accumulation of carbonaceous deposits. Even if such deactivation is shown to be reversible (regeneration by oxidative treatment), it is more attractive to prevent it from happening. Studying the effect of gas doping, we show that introducing a small fraction of oxygen (0.44 vol%) leads to a marked decrease of the extent of coking and stabilization of catalytic activity at a much higher conversion level (75% after 24 h). A slightly higher O₂ concentration (1.77 vol%) leads to complete stabilization of the ethanol conversion (90% after 24 h), but concomitantly provokes a slight drop in acetaldehyde selectivity. With the findings of this study, with optimized reaction conditions and an ameliorated catalyst formulation, an outstanding acetaldehyde productivity (2.9 g_aca g_cat⁻¹ h⁻¹) was maintained fully stable for 24 h.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770990","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":"Unveiling the relation between multiple chemical products and process conditions for trichloroethylene and perchloroethylene production via catalysis network analysis†","authors":"","doi":"10.1039/d4cy00573b","DOIUrl":"10.1039/d4cy00573b","url":null,"abstract":"<div><p>Trichloroethylene (TRI) and perchloroethylene (PER) are widely-produced in the chemical industry and used as solvents, varnishes, degreasers, and dry cleaning chemicals that involve complex process conditions. Data science and network analysis are used in order to unveil relationships between reactants, process conditions, and selectivities of select products with the aim to improve production efficiency. Data visualization and machine learning reveal the sets of conditions that have positive and inverse relations with TRI and PER selectivities, while transforming the data into networks reveals which sets of experimental conditions correlate with desired outcomes. Thus, it becomes possible to tailor experimental conditions in order to increase desired selectivities while avoiding production of undesirable selectivities.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141771057","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":"Design, synthesis, and applications of plasmonic semiconductor WO3− x photocatalyst","authors":"","doi":"10.1039/d4cy00645c","DOIUrl":"10.1039/d4cy00645c","url":null,"abstract":"<div><p>Localized surface plasmon resonance (LSPR) facilitates solar-to-chemical conversion, which is a rapidly expanding field that effectively harnesses solar energy because of its distinct catalytic and optical responses. Plasmonic WO_{3− x} exhibits great potential to absorb NIR light of the solar spectrum owing to LSPR. WO_{3− x} also exhibits tremendous potential in the field of photocatalysis because of its exceptional features, which include low toxicity, low cost, excellent carrier mobility, stability, and ease of synthesis. In this report, we have discussed the different synthesis techniques for WO_{3− x} photocatalysts, the tunability to enhance light absorption and the accelerating transfer of charge carriers. This review further emphasizes recent developments in the applications of plasmonic semiconductor WO_{3− x} nanostructures in hydrogen generation from water splitting and ammonia borane (AB) dehydrogenation, CO₂ reduction, organic transformations, and pollutant degradation under visible-NIR light illumination. The fundamental mechanisms for increased catalytic activities, as well as the rational design of hybrid WO_{3− x} nanocatalysts, have been discussed. The present obstacles and potential future directions have also been explored to advance plasmon-mediated heterogeneous catalysis toward practical applications. This article aims to provide a thorough understanding of synthesis, modification, and recent developments in the application of NIR light-driven catalysis of WO_{3− x} materials.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141872294","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":"Influence of binders and matrices on zeolite-containing catalysts","authors":"","doi":"10.1039/d4cy00737a","DOIUrl":"10.1039/d4cy00737a","url":null,"abstract":"<div><p>Industrial solid catalysts are rarely pure materials consisting solely of catalytically active species; many are complex multiphase composites. This complexity is exemplified by zeolite catalysts, which are widely applied in industry. Given the proprietary nature of industrial catalysis, the fundamental chemistry and materials science of binder-catalyst combinations have been largely neglected. Although binders might be considered to be inert components, they often significantly influence catalyst behavior. Over the preceding decade, academic awareness has increased significantly, bridging the knowledge gap between fundamental zeolite research and the practical use of zeolite catalysts. Building on these advances, we aim to summarize the state of this field, focusing on understanding of the role of binders in zeolite catalysts, both with and without metals, and presenting insights into how binders affect acid density, porosity, and the control of the proximity between metal and acid sites within shaped zeolite catalysts. We anticipate that binders will continue to play crucial roles in zeolite catalysis and offer a perspective on emerging topics and recommendations for future work on the subject.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141936831","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":"Recent advances in selective methanol oxidation electrocatalysts for the co-production of hydrogen and value-added formate","authors":"Jiaxin Li, Hongmei Yu, Jingchen Na, Senyuan Jia, Yutong Zhao, Kaiqiu Lv, Wenzhuo Zhang, Jun Chi, Zhigang Shao","doi":"10.1039/d4cy00727a","DOIUrl":"https://doi.org/10.1039/d4cy00727a","url":null,"abstract":"Traditional water splitting is significantly impeded by the sluggish kinetics and large overpotential of the anodic oxygen evolution reaction (OER). Accordingly, replacing the OER with a more thermodynamically favorable organic substance oxidation reaction to combine with the hydrogen evolution reaction (HER) is an innovative strategy to obtain green hydrogen. In this case, the electro-reforming of methanol coupled with the electrochemical HER can realize the energy-saving co-generation of value-added formate and hydrogen. Therefore, controlling the process of methanol oxidation and making it selectively transform to formate have become a worthy topic. Thus far, various catalysts and modification strategies have been developed for the selective methanol oxidation reaction (SMOR). Transition metal-based materials are the most studied catalysts because their moderate catalytic ability can better control the process of methanol oxidation. Electronic structure modulation is the most efficient strategy to improve the SMOR performance of catalysts. However, few systematic reviews on the SMOR have been reported. In light of significant advances achieved recently, herein, we reviewed the recent advances in SMOR electrocatalysts for the co-production of value-added formate and green hydrogen. In particular, the mechanism of the SMOR is initially introduced, including the traditional surface adsorption mechanism and the newly developed lattice oxygen participation mechanism. Subsequently, strategies for catalyst design are analyzed from the aspects of chemical bond activation/inhibition, electronic structure manipulation, dual active site construction, and increasing the number of active sites. Thereafter, performance descriptors involving electrochemical measurements and product detection are discussed to show the basic evaluation criterion, and various catalysts for the SMOR are categorized according to their composition to display the development of catalysts. Finally, conclusions and perspectives are presented. We hope that this comprehensive effort will be helpful in the literature survey of the SMOR and provide inspiration to the SMOR research community, attracting more attention to the electro-upgradation of organic substances coupled with green hydrogen generation.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205466","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}