Catalysis Science & Technology最新文献

{"title":"Experimental and DFT study of the MoO2@Fe2O3 catalyst for overall water splitting in acidic and alkaline electrolytes","authors":"Suchitra N. Sapakal ,&nbsp;Arvind Singh ,&nbsp;Ayesha Khan ,&nbsp;Mayur Gaikwad ,&nbsp;Jin H. Kim ,&nbsp;Anamika Kadam","doi":"10.1039/d4cy00779d","DOIUrl":"10.1039/d4cy00779d","url":null,"abstract":"<div><div>Energy is an essential component of human life. Among the various forms of energy generation, water splitting using electricity is a non-polluting green method that produces both hydrogen and oxygen. This research presents a unique methodology involving the hydrothermal synthesis of MoO₂@Fe₂O₃ on a stainless steel (SS) substrate, aimed at facilitating overall water splitting in both acidic and alkaline environments. Various analytical techniques, including XRD, SEM, FE-SEM, FTIR, and UV-vis DRS, were utilized to characterize the structural, morphological, and optical properties of the synthesized materials. We also employed density functional theory (DFT) to calculate the work of adhesion and bulk modulus for MoO₂, Fe₂O₃ and MoO₂@Fe₂O₃. Comparative electrochemical analysis revealed that the MoO₂@Fe₂O₃ thin films exhibited reduced overpotential for overall water splitting in KOH compared to that in H₂SO₄ electrolytes. Specifically, in KOH and H₂SO₄ electrolytes, the films demonstrated cell voltages of 1.75 V <em>vs.</em> RHE and 1.80 V <em>vs.</em> RHE, respectively. Moreover, Tafel slopes were observed to be lower in acid electrolytes than in alkaline electrolytes. Regarding stability, the interfaced electrode displayed promising performance, with 14 hours and 8 hours of stability for the OER and HER, respectively, in the KOH electrolyte, and 12 hours and 6 hours of stability for the HER and OER, respectively, in the H₂SO₄ electrolyte. We determined the interfacial work of adhesion and bulk modulus using DFT, which suggested a stable interfacial structure for MoO₂@Fe₂O₃. This confirms the drifting of Mo atoms towards Fe atoms, resulting in the production of oxygen vacancies, which create a mid-band gap, suggesting good metallic range conductivity, which is also evident from the decreased band gap value for MoO₂@Fe₂O₃. DFT studies together with experimental results propose a new strategy offering great possibilities to tune the selectivity of photo-catalytically active metal oxide materials.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 23","pages":"Pages 6934-6946"},"PeriodicalIF":4.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142694700","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":"Enhancing coking resistance of nickel-based catalysts for dry reforming of methane via nitric oxide abatement: a support study†","authors":"Beatrice Senoner, Andrea Osti and Antonella Glisenti","doi":"10.1039/D4CY00936C","DOIUrl":"https://doi.org/10.1039/D4CY00936C","url":null,"abstract":"<p >Coking poses a significant challenge to the longevity and efficacy of catalysts in dry reforming of methane (DRM), particularly for nickel-based catalysts, which are widely used for their affordability and high catalytic activity. This study explores a recent approach integrating DRM with NO reduction to address coking-related deactivation, aiming to gasify carbon deposits and reduce NO simultaneously. Therefore, herein, NO conversion is achieved using the carbon undesired by-product of the DRM reaction, avoiding the use of valuable resources for NO conversion (such as NH<small>₃</small>), <em>via</em> an approach “from waste to value” that enhances the sustainability of the process. Four nickel-impregnated oxide supports (γ-Al<small>₂</small>O<small>₃</small>, MgAl<small>₂</small>O<small>₄</small> coated γ-Al<small>₂</small>O<small>₃</small>, CaZrO<small>₃</small>, and LaFeO<small>₃</small>) were compared to understand the key properties of catalyst design. The best performances were obtained for supports with a high surface area and high interaction with metal particles (95% reactant conversion for Ni/γ-Al<small>₂</small>O<small>₃</small>) as they allowed stable activity and protection from NO oxidation. Supports with a lower surface area suffered from coke blockage of active sites, whereas no protection from oxidation led to complete deactivation of the active phase. The LaFeO<small>₃</small> support stood out for its ability to protect Ni from NO oxidation by reducing NO. Overall, this study showed the importance of balancing NO oxidative power and coking issues, emphasizing the relevance of catalyst design in both protecting Ni from NO oxidation and avoiding coke blockage of the active sites <em>via</em> high surface area supports.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6678-6691"},"PeriodicalIF":4.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00936c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598665","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":"Predicting the effect of framework and hydrocarbon structure on the zeolite-catalyzed beta-scission†","authors":"Yannick Ureel, Konstantinos Alexopoulos, Kevin M. Van Geem and Maarten K. Sabbe","doi":"10.1039/D4CY00973H","DOIUrl":"10.1039/D4CY00973H","url":null,"abstract":"<p >Developing improved zeolites is essential in novel sustainable processes such as the catalytic pyrolysis of plastic waste. This study used density functional theory to investigate how alkyl chain length, unsaturated bonds, and branching affect β-scission kinetics in four zeolite frameworks, a key reaction in hydrocarbon cracking. The activation enthalpy was evaluated for a wide variety of 23 hydrocarbons, with 6 to 12 carbon atoms, in FAU, MFI, MOR, and TON. The consideration of both branched and linear olefin and diolefin reactants for the β-scission indicates how the reactant structure influences the intrinsic cracking kinetics, which is especially relevant for the catalytic cracking of plastic waste feedstocks. Intrinsic chemical effects, such as resonance stabilization, the inductive effect, and pore stabilization were found to provide an essential contribution to the activation enthalpy. Additionally, a predictive group additive model incorporating a novel so-called “pore confinement descriptor” was developed for fast prediction of the β-scission activation barrier of a wide range of molecules in the four zeolites. The obtained model can serve as an input for detailed kinetic models in zeolite-catalyzed cracking reactions. The acquired fundamental insights in the cracking of hydrocarbons, relevant for renewable feedstocks, correspond well with experimental observations and will facilitate an improved rational zeolite design.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7020-7036"},"PeriodicalIF":4.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11474451/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453596","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":"Unspecific peroxygenase immobilization in 3D-printed microfluidics: towards tailor-made screening platforms†","authors":"Elena Gkantzou, Theofilia Koulopoulou, Hannah Brass, David Schönauer, Anton Glieder and Selin Kara","doi":"10.1039/D4CY00869C","DOIUrl":"https://doi.org/10.1039/D4CY00869C","url":null,"abstract":"<p >In the context of empowering biocatalysis, an easy-to-develop, reproducible, and easy-to-scale biocatalytic system under continuous flow is demonstrated. 3D printing technology is used as the reactor manufacturing method, yielding identical and low-cost microfluidic chips that can be further modified to serve as a biocatalytic platform for simultaneous parameter screening. The model enzyme studied here is unspecific peroxygenase (UPO). UPOs are currently under intensive study, due to their distinct promiscuity in oxyfunctionalization chemistry. This is the first study demonstrating UPO's immobilization in a microfluidic concept. The developed method for surface functionalization of microfluidic reactors is based on polydopamine modification and was proven highly reproducible. UPO showed a TTN of 19 249 and a STY of 2.1 g L<small>⁻¹</small> h<small>⁻¹</small>, under the specified conditions. The kinetic behavior of the system under flow conditions is reported. The system was also regenerated with a 51.4% recovered activity. Further utilization of microfluidic concepts is expected to unravel the full potential of UPOs for oxyfunctionalization reactions of particular interest. The proposed system is foreseen as a screening platform for different reaction conditions, reaction substrates, or enzyme mutants.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6496-6502"},"PeriodicalIF":4.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598702","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":"One-pot synthesis of 1,4-butanediol via the deep hydrogenation of maleic anhydride over Cu–xMo/SiO2 catalysts†","authors":"Kai Cui, Jiaming Yang, Yuli Jing, Junwen Chen, Chen Zhao, Peng Wu and Xiaohong Li","doi":"10.1039/D4CY01006J","DOIUrl":"https://doi.org/10.1039/D4CY01006J","url":null,"abstract":"<p >Sustainability issues have led to a gradual market expansion for the 1,4-butanediol (BDO) monomer of the biodegradable plastics to replace conventional plastics. Maleic anhydride (MA) can be derived from the oxidation of bio-based furfural or fructose. Although the hydrogenation of MA can produce a series of products, including succinic anhydride (SA), γ-butyrolactone (GBL), BDO and tetrahydrofuran (THF), the one-pot deep hydrogenation of MA to BDO or THF under mild conditions has been rarely reported in the literature until now. Herein, we report the production of BDO from the one-pot deep hydrogenation of MA over a Cu–0.03Mo/SiO<small>₂</small> catalyst, achieving 100% MA conversion and 88.3% BDO yield. The Cu–0.03Mo/SiO<small>₂</small> catalyst also showed good long-term stability without obvious loss in activity or BDO selectivity during a 160 h time-on-stream test. Doping Mo to Cu/SiO<small>₂</small> catalysts in an optimal amount adjusted the distribution of Cu<small>⁰</small>/Cu<small>⁺</small> species and modulated the interaction of Cu–SiO<small>₂</small> and surface acidity, so that the activation of hydrogen, MA and relevant intermediates can become balanced, in addition to the restriction of side-reactions. This study provides potential for the green synthesis of BDO with non-precious Cu-based catalysts.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 24","pages":" 7081-7092"},"PeriodicalIF":4.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798119","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":"Acrylamides from 1,2-dichloroethane via palladium-catalyzed carbonylation†","authors":"Ren-Rui Xu, Chang-Sheng Kuai and Xiao-Feng Wu","doi":"10.1039/D4CY01117A","DOIUrl":"https://doi.org/10.1039/D4CY01117A","url":null,"abstract":"<p >1,2-Dichloroethane, a widely produced chemical raw material, has attracted considerable attention due to its versatility in various applications. Herein, we report an efficient strategy for the synthesis of acrylamides <em>via</em> palladium-catalyzed carbonylation, using 1,2-dichloroethane and amines as starting materials. The catalytic system demonstrated remarkable tolerance towards a broad range of amines, producing the corresponding acrylamides in good to excellent yields. Remarkably, a variety of aromatic and alkyl amines were completely converted within 40 minutes, delivering the target products with an impressive 99% yield. Additionally, the strategy's versatility was confirmed by its successful application in the synthesis of functionalized acrylates. Importantly, the reaction was scaled up to 1 mmol scale with consistent yields, underscoring its potential for practical use in organic synthesis.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6180-6185"},"PeriodicalIF":4.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy01117a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524271","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":"Study on the effect and mechanism of Ag and Bi2MoO6 modification on the CO2 photo-thermal reduction performance of g-C3N4 catalysts with localized surface plasmon resonance†","authors":"Bin Guan, Junyan Chen, Zhongqi Zhuang, Zhan Gao, Zeren Ma, Xuehan Hu, Chenyu Zhu, Sikai Zhao, Kaiyou Shu, Hongtao Dang, Tiankui Zhu and Zhen Huang","doi":"10.1039/D4CY00930D","DOIUrl":"https://doi.org/10.1039/D4CY00930D","url":null,"abstract":"<p >As a promising future energy material, g-C<small>₃</small>N<small>₄</small> as a CO<small>₂</small> photo-thermal-reduction catalyst can effectively convert CO<small>₂</small> to renewable fuel, but the low yield and low product selectivity significantly limit its further development and application. Herein, Ag and Bi<small>₂</small>MoO<small>₆</small> were loaded separately or together on g-C<small>₃</small>N<small>₄</small> catalysts by photo-deposition and solvothermal synthesis methods, wherein the conversion efficiency of the g-C<small>₃</small>N<small>₄</small> catalyst co-loaded with 0.5% Ag and 10% Bi<small>₂</small>MoO<small>₆</small> was the highest (CO yield = 50.77 μmol g<small>⁻¹</small> h<small>⁻¹</small>, CO selectivity = 96.98%). Characterization shows that the co-loading of Ag and Bi<small>₂</small>MoO<small>₆</small> reduces the band gap of g-C<small>₃</small>N<small>₄</small>, improves the light absorption performance, and promotes the photoelectron transfer and CO<small>₂</small> adsorption, which may be attributed to the LSPR of Ag and the Z-scheme heterojunction between g-C<small>₃</small>N<small>₄</small> and Bi<small>₂</small>MoO<small>₆</small>. The results of <em>in situ</em> DRIFTS and DFT calculations are consistent with the above conclusion and show that Ag loading effectively reduces the energy barrier of each intermediate state. This thesis aims to provide data support and theoretical guidance for optimal design of g-C<small>₃</small>N<small>₄</small> catalysts.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6621-6640"},"PeriodicalIF":4.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598660","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":"Photocatalytic H2O2 production with perylene(bis-imide)-doped periodic mesoporous silica using micropollutants as sacrificial donors†","authors":"Charlotte David, Stephane Grolleau, Denys Grekov, Aydar Rakhmatullin, Errol Blart, Valerie Hequet and Yann Pellegrin","doi":"10.1039/D4CY00739E","DOIUrl":"https://doi.org/10.1039/D4CY00739E","url":null,"abstract":"<p >A perylene-doped mesoporous silica material, PDI-SiO<small>₂</small>, is used as a heterogeneous photocatalyst for the light-driven production of H<small>₂</small>O<small>₂</small> from polluted water samples. The photocatalyst operating principle is based on a reductive quenching mechanism where aqueous micropollutants act as sacrificial donors. The resulting reduced photocatalyst transfers electrons to aqueous O<small>₂</small>, leading to superoxide O<small>₂</small>˙<small>⁻</small>, which evolves into H<small>₂</small>O<small>₂</small>. Using a set of representative micropollutants (diclofenac, bisphenol-A and ofloxacin), appreciable amounts of H<small>₂</small>O<small>₂</small> have been photoproduced (from 0.2 to 1.7 mM over 8 hours of irradiation) from concentrated samples (1 mM). Less concentrated samples (10 μM) were efficiently decontaminated when treated with PDI-SiO<small>₂</small> in the presence of Fenton catalysts. We evidence that the efficiency of H<small>₂</small>O<small>₂</small> photoproduction is related to the extent of the interactions between micropollutants and PDI-SiO<small>₂</small>.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6710-6719"},"PeriodicalIF":4.4,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598748","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":"Highly effective solar CO2 fixation via photocatalytic carboxylation of aromatic amines with carbon dioxide over a covalent organic framework (COF) as a photocatalyst†","authors":"Chandani Singh, Jae Young Kim, No-Joong Park, Rajesh Kumar Yadav and Jin-Ook Baeg","doi":"10.1039/D4CY00949E","DOIUrl":"https://doi.org/10.1039/D4CY00949E","url":null,"abstract":"<p >Carbon dioxide (CO<small>₂</small>) is an attractive building block in terms of abundance and sustainability. However, the low reactivity of CO<small>₂</small> limits its application in organic reactions as frequently high-energy reagents are needed to drive organic transformation. Here, we report the efficient carboxylation of aromatic amines with CO<small>₂</small> in the presence of a covalent organic framework (COF) as a photocatalyst in combination with a nickel(<small>II</small>) complex as a co-catalyst under solar light irradiation. This solar-light photo-catalyzed strategy provides a facile method to produce a series of valuable carboxylic acids. Moreover, this versatile protocol shows an inexpensive photocatalyst, mild reaction conditions, and good functional group tolerance without the necessity of using stoichiometric metallic reductants. Moderate to good yields of the desired carboxylic acids were obtained in a substrate scope. This method opens new opportunities for the carboxylation of aromatic amines with CO<small>₂</small>.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 22","pages":" 6670-6677"},"PeriodicalIF":4.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598664","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":"Photocatalytic dehydrogenative C(sp2)–P coupling reaction between dibenzo[b,f][1,4]oxazepanes and phosphine oxides†","authors":"Zhaotian Wu, Xuefei Sha, Shan Wang, Huan Yang, Shaojun Zheng, Chunhui Jiang, Shu-Yang Chen and Hongfei Lu","doi":"10.1039/D4CY00955J","DOIUrl":"https://doi.org/10.1039/D4CY00955J","url":null,"abstract":"<p >Visible-light-induced cross-dehydrogenative coupling between heptameric cyclic imine derivatives and diaryl phosphine oxides has been developed and heptameric cyclic imine phosphate derivatives have been synthesized by using rhodamine B as a photocatalyst. Transition metal-free catalysis, green synthesis and efficient synthesis under ambient conditions are attractive aspects of the method.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 21","pages":" 6176-6179"},"PeriodicalIF":4.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524270","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}