Catalysis Science & Technology最新文献

{"title":"Theoretical study of reductive CO2 functionalization with amines and phenylsilanes: what kind of solvents can be used as catalysts?†","authors":"Pan Du, Xinyue Liu, Xinyi Dong, Nianyang Li, Rui Liu, Li Li and Jiyang Zhao","doi":"10.1039/D3CY00682D","DOIUrl":"https://doi.org/10.1039/D3CY00682D","url":null,"abstract":"<p >In this study, the mechanisms of CO<small>₂</small> formylation and methylation with <em>N</em>-methylaniline and PhSiH<small>₃</small> were investigated using density functional theory (DFT) calculations, and the chemical selectivity of the reaction towards formamide or methylamine products was analyzed. The solvent <em>N</em>,<em>N</em>-dimethylformamide (DMF) served as both the solvent and catalyst. The obtained computational results indicated that both reactions are initiated by three successive CO<small>₂</small> reduction steps with hydrosilane to give a stable species, triformyloxysilane [Si](OCHO)<small>₃</small>. Subsequently, formamides are generated upon the formylation of amines with the reduced CO<small>₂</small> at low temperatures. At high temperatures, methylation occurs <em>via</em> a key formaldehyde intermediate, leading to <em>N</em>,<em>N</em>-dimethylaniline. Based on the relationship between free energy barriers and the Hirshfeld charges of oxygen atoms in the solvents, the generic structures of solvents that can effectively promote the reduction of CO<small>₂</small> with phenylsilane are given. These solvents have a negatively charged oxygen atom with a Hirshfeld charge less than or equal to −0.28.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5333-5344"},"PeriodicalIF":5.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164168","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":"Observation of reactive intermediates in the initial stage during ethene conversion over acidic zeolites†","authors":"Jing Niu, Yu-Ting Miao, Wei David Wang, Meng-Tong Ruan, Zhi-Peng Wang, Hua-Dong Xue, Si-Min Yu, Chong Liu, Jian-Feng Wu and Wei Wang","doi":"10.1039/D3CY00709J","DOIUrl":"https://doi.org/10.1039/D3CY00709J","url":null,"abstract":"<p >The key intermediates, <em>i.e.</em>, surface ethoxy species, were observed upon the adsorption of ethene on zeolite H-Y for the first time. By combining a selective <small>¹³</small>C-labeling protocol with a multitechnique approach, we confirmed the critical role of surface ethoxy species, that is, equilibrium with ethene in the primary step and further alkylation to form the C–C bond.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 17","pages":" 4926-4931"},"PeriodicalIF":5.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"3570217","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":"Density functional theory calculation of two-dimensional transition metal–hexaiminotriphenylene (TM-HITP) electrocatalytic CO2 reduction†","authors":"Xianshi Zeng, Luliang Liao, Meishan Wang and Hongming Wang","doi":"10.1039/D3CY00879G","DOIUrl":"https://doi.org/10.1039/D3CY00879G","url":null,"abstract":"<p >Carbon dioxide reduction technology can solve the shortage of resources and climate issues like “warming of the planet”. Metal–organic frameworks (MOFs) contain well-defined active sites, a huge specific surface, and a robust porous structure, making them a good candidate for use in CO<small>₂</small> electrocatalytic reduction. Using the principles of spin-polarization density functional theory, the two-dimensional MOF constructed from transition metal–hexaiminotriphenylene was calculated to reduce CO<small>₂</small> electrocatalytically. The results show that for ten transition metal (TM-HITP) two-dimensional network structures spanning Sc through Zn, the formation energies <em>E</em><small>_f</small> are all negative, and they can theoretically be synthesised experimentally, and the metal atoms can be disseminated in the HITP framework steadily because their binding energies to HITP are highly sufficient. Considering the competition with the HER, all catalysts showed CO<small>₂</small>RR selectivity except Co-HITP. Co-HITP catalysts required pH &gt;7.22 to show CO<small>₂</small>RR selectivity. The main products and overpotentials of both Fe and Co catalysts were in agreement with the available literature values, indicating that the calculations were reliable. HCOOH is the primary product for Sc, Ni, and Cu. The principal product of Ti and V is CH<small>₄</small>. CH<small>₃</small>OH is the primary product for Cr, Fe, and Co. The product selectivity of Mn was poor and three products, CH<small>₄</small>, HCHO and HCOOH, were obtained simultaneously at the same limiting potential. The limiting potentials of these ten catalysts for electrocatalytic CO<small>₂</small> reduction ranged from 0.296 to 0.738 volts and the overpotentials between 0.027 V and 0.754 V, all of which were rather little. Consequently, we forecast that the two-dimensional MOFs constructed with transition metals with hexaiminotriphenylene are potential electrocatalysts for CO<small>₂</small> reduction because they demonstrate excellent catalytic activity in the electrocatalytic reduction of CO<small>₂</small>.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5351-5364"},"PeriodicalIF":5.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164170","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 structure-sensitive descriptor for the design of active sites on MoS2 catalysts†","authors":"Hai-Yan Su, Federico Calle-Vallejo and Keju Sun","doi":"10.1039/D3CY00575E","DOIUrl":"https://doi.org/10.1039/D3CY00575E","url":null,"abstract":"<p >MoS<small>₂</small> catalysts hold great promise for numerous reactions of industrial and technological interest. However, general guidelines for the design of their active sites remain elusive. We hypothesize that this is because the link between their geometric structure and reactivity is yet to be established at the atomic scale. Here we show that cn, a metric based on the number of sulfur atoms coordinated to Mo atoms, captures the trends in reactivity of MoS<small>₂</small> catalysts with various sulfur vacancy contents. This is illustrated for the adsorption energies of numerous monatomic and polyatomic species. More importantly, cn can be used to predict the reaction and activation energies of common formation and dissociation reactions in catalysis. Finally, cn is used to outline the optimal configuration of MoS<small>₂</small> active sites for the electrocatalytic hydrogen evolution reaction: the highest exchange current density corresponds to terrace sites with adjacent S vacancies with cn in the range of 4.33 to 4.67.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5290-5300"},"PeriodicalIF":5.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164164","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":"Reactivity and stability synergism directed by the electron transfer between polyoxometalates and metal–organic frameworks†","authors":"Xinlin Lu, Ting Cheng, Yurii V. Geletii, John Bacsa and Craig L. Hill","doi":"10.1039/D3CY00569K","DOIUrl":"https://doi.org/10.1039/D3CY00569K","url":null,"abstract":"<p >The synergism between polyoxometalates (POM) and Cu(<small>II</small>) ions in homogeneous aerobic thiol oxidative deodorization has been realized in a more utilitarian heterogeneous catalyst: a multi-electron-capable POM captured in the pores of a metal–organic framework (MOF), HKUST-1 (POM@HKUST). The synergism between POM and the Cu(<small>II</small>) nodes in the MOF depends on the type of POM. Phosphovanadomolybdates, PV<small>_<em>x</em></small>Mo<small>_{12−<em>x</em>}</small>O<small>₄₀</small><small>^{(3+<em>x</em>)−}</small> (<em>x</em> = 1–3) (<strong>PVMo</strong>) but not transition-metal-substituted polytungstates <strong>PXW</strong><small>_{<strong>11</strong>}</small> (X = V, Co, Zn and Co) result in POM@MOF materials that exhibit synergy relative to the individual structural components, the POM or MOF alone, not only for reactivity as in the case for the analogous homogeneous catalysts, but also for catalyst structural stability. The <strong>PVMo</strong>@HKUST-catalyzed reaction proceeds to essentially 100% conversion and the material is recoverable and unchanged based on FTIR spectroscopy, powder XRD data and other observations after reaction. The <strong>PXW</strong><small>_{<strong>11</strong>}</small>@HKUST materials produce only limited conversions and decompose to white powders after reaction. X-ray photoelectron spectroscopy reveals that all the Cu(<small>II</small>) sites in the HKUST-1 become Cu(<small>I</small>) sites that are stable in air. Further kinetics studies show that <strong>PVMo</strong> undergoes fast multielectron transfer with intermediate Cu/RSH complexes, while <strong>PXW</strong><small>_{<strong>11</strong>}</small> show far slower and limited electron transfer ability with these Cu/RSH complexes. Limited electron transfer between Cu nodes and the encapsulated POM units not only hinders reactivity but also leads to MOF framework distortion and subsequent decomposition induced by the reduction of Cu(<small>II</small>) to Cu(<small>I</small>) sites in the framework.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 17","pages":" 5094-5103"},"PeriodicalIF":5.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/cy/d3cy00569k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"3938919","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":"CeO2-supported Ni and Co catalysts prepared by a solution combustion method for H2 production from glycerol: the effect of fuel/oxidizer ratio and oxygen excess†","authors":"Anna N. Matveyeva, Shamil O. Omarov, Marianna A. Gavrilova, Andrey D. Trofimuk, Johan Wärnå and Dmitry Yu. Murzin","doi":"10.1039/D3CY00854A","DOIUrl":"https://doi.org/10.1039/D3CY00854A","url":null,"abstract":"<p >Glycerol is a promising raw material for obtaining various chemicals and fuels, including H<small>₂</small>. Nevertheless, the development of cost-effective and stable catalysts with high activity and selectivity for H<small>₂</small> production from glycerol under mild conditions has been a serious problem for their practical use. In this work, a series of CeO<small>₂</small>-supported Ni and Co catalysts with the content of Ni and Co as metal(<small>II</small>) oxides being 30 wt% was prepared by solution combustion synthesis <em>via</em> changing the fuel/oxidizer ratio (<em>φ</em> = 0.7–3), the fuel type (glycine, urea), and the oxygen excess. Thus, various species of Ni and Co and their interactions with CeO<small>₂</small> were obtained, which affected the reduction sequence, defectiveness, textural characteristics, and activity in steam and aqueous-phase reforming of glycerol. To study the characteristics of the obtained samples, instrumental methods such as XRD, DTA-TGA, low-temperature N<small>₂</small> physisorption, SEM-EDX, H<small>₂</small>-TPR, and H<small>₂</small>- and CO<small>₂</small>-TPD, as well as Raman spectroscopy, were used. The results demonstrated that the Ni–Ce–O system synthesized with a high glycine-to-oxidizer ratio can successfully compete with catalysts based on noble metals (Pt/γ-Al<small>₂</small>O<small>₃</small>) in aqueous-phase reforming of glycerol.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5387-5406"},"PeriodicalIF":5.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/cy/d3cy00854a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164184","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":"NHC-catalyzed enantioselective radical reactions of enal and pyridinium salt: mechanism and origin of regio- and stereoselectivities†","authors":"Kuohong Chen, Jiaming Zhang, Qianqian Shi, Lili Han, Dongmin Fu, Donghui Wei and Yanyan Zhu","doi":"10.1039/D3CY00791J","DOIUrl":"https://doi.org/10.1039/D3CY00791J","url":null,"abstract":"<p >Understanding the origin of regio- and stereoselectivities of radical reactions remains a great challenge in radical chemistry. To address this, we conducted density functional theory calculations to investigate the possible mechanisms and origin of selectivities of N-heterocyclic carbene (NHC)-catalyzed enantioselective radical reactions of enals and pyridinium salts. Our findings suggest that the energetically favorable pathway involves a series of steps, including nucleophilic attack of NHC on enal, [1,2]-proton transfer, diradical generation <em>via</em> relayed-PCET, stereoselective C–C bond formation, [1,5]-HAT, N–N σ-bond homolysis, [1,3]-proton transfer, esterification, and regeneration of the NHC catalyst. NCI and AIM analysis revealed that C–H⋯Cl and C–H⋯π interactions are the primary factors controlling stereoselectivity. We conducted multiple analyses to explore the nature of the radical transformation processes. Overall, our study provides insight into the detailed mechanisms and origin of regio- and stereoselectivities in these kinds of NHC-catalyzed radical reactions and serves as a valuable case study for theoretical investigations on radical reactions.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5259-5266"},"PeriodicalIF":5.0,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164147","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":"In situ construction of a Sillén–Aurivillius layered perovskite-based 0D/2D homologous Schottky junction for efficient piezo-photocatalytic activity†","authors":"Jian Yang, Yali Xue, Chuang Han, Xiaorui Zhang, Ke Sa, Jin Jia, Hanlin Ye and Yujun Liang","doi":"10.1039/D3CY00876B","DOIUrl":"https://doi.org/10.1039/D3CY00876B","url":null,"abstract":"<p >The interface shielding effect resulting from the accumulation of charge carriers and the relatively weak driving force provided by the single built-in electric field in conventional heterojunctions seriously hamper the rapid and continuous charge separation. Herein, focusing on Sillén–Aurivillius perovskite-type bismuth tantalum oxyhalides, an ingenious 0D/2D Bi/Bi<small>₄</small>TaO<small>₈</small>Cl<small>_0.5</small>Br<small>_0.5</small> (BTOCB) piezoelectric homologous Schottky heterojunction is judiciously designed and fabricated <em>via in situ</em> deposition of Bi nanodots on the surfaces of BTOCB solid solution nanosheets and shows mainly exposed (001) facets and strong piezoelectricity. Rietveld refinements confirm the substitution of Cl and Br in the lattice, and the band structure is regulated by solid solution engineering. Meanwhile, the introduction of Bi improves visible light absorption and creates an internal electric field at the heterointerface. Under the synergetic action of illumination and ultrasonic vibration, the unique multi-internal electric field modulation derived from the piezoelectric polarization and Schottky junction can break the heterointerface shielding effect and deliver powerful driving force for impactful spatial photocarrier migration and separation. As a result, the as-prepared Bi/BTOCB Schottky junction exhibits outstanding piezo-photocatalyst performance for tetracycline (TC) degradation. Lastly, the possible degradation pathway of TC is proposed, and the toxicity of intermediates is also analyzed. This study demonstrates a strategy of multi-field modulation in optimizing photogenerated carrier behaviors and gives deep insights into the design of high-performance piezo-photocatalysts.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5313-5325"},"PeriodicalIF":5.0,"publicationDate":"2023-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164166","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":"Steering ammonia decomposition over Ru nanoparticles on ZrO2 by enhancing metal–support interaction†","authors":"Tong Zhang, Xiaohua Ju, Lvye Liu, Lin Liu, Teng He, Yunhua Xu, Hanying Wang and Ping Chen","doi":"10.1039/D3CY00691C","DOIUrl":"https://doi.org/10.1039/D3CY00691C","url":null,"abstract":"<p >ZrO<small>₂</small>, one of the typical oxides, holds promise as a support for supported metal-based catalysts. Herein, Ru nanoparticles (NPs) on ZrO<small>₂</small> (Ru/ZrO<small>₂</small>) analogues were prepared from milling and precipitation methods and applied in ammonia decomposition reaction. It was found that the Ru NPs in different Ru/ZrO<small>₂</small> samples possessed similar particle sizes. Under identical reaction conditions, the Ru/ZrO<small>₂</small> obtained from precipitation methods exhibits much higher activity than the Ru/ZrO<small>₂</small> analogue with nearly identical Ru NPs on ZrO<small>₂</small> obtained from the milling method. A hydrogen formation rate of 1439 mmol g<small>_cat</small><small>⁻¹</small> h<small>⁻¹</small> and excellent stability were achieved over Ru/ZrO<small>₂</small> catalyst from the precipitation method at 450 °C with a space velocity of 30 000 mL g<small>_cat</small><small>⁻¹</small> h<small>⁻¹</small>, comparable with many efficient Ru-based catalysts reported previously. The characterization results reveal that the superior catalytic performance of Ru/ZrO<small>₂</small> from the precipitation method was mainly attributed to the modulated electronic structure of Ru NPs, which stems from the intimate interaction between Ru NPs and the ZrO<small>₂</small> support. As a result, Ru/ZrO<small>₂</small> from the precipitation method can facilitate the activation and dissociation of NH<small>₃</small> molecules and exhibit greatly enhanced activity and intrinsic activity for NH<small>₃</small> decomposition. This work offers opportunity for improving the catalyst performance by regulating the metal–support interaction of Ru-based NH<small>₃</small> decomposition catalysts.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5205-5213"},"PeriodicalIF":5.0,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164143","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":"Selective aerobic oxidation of biomass model compound veratryl alcohol catalyzed by air-stable copper(ii) complexes in water†","authors":"Narayan Ch. Jana, Sourav Behera, Suraj Kumar Maharana, Rakesh R. Behera and Bidraha Bagh","doi":"10.1039/D3CY00671A","DOIUrl":"https://doi.org/10.1039/D3CY00671A","url":null,"abstract":"Air-stable square pyramidal copper(II)–bromide complexes 1, 2 and 3 with NNS, N(NH)S and NNO ligand frameworks, respectively, were synthesized and successfully utilized as effective catalysts for the aerobic oxidation of...","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 18","pages":" 5422-5434"},"PeriodicalIF":5.0,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"7164186","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}