Catalysis Science & Technology最新文献

{"title":"Multistep screening of transition-metal-based homonuclear double-atom catalysts to unravel the electronic origin of their activity and selectivity challenges for nitrogen reduction†","authors":"Anjumun Rasool ,&nbsp;Manzoor Ahmad Dar","doi":"10.1039/d4cy00480a","DOIUrl":"10.1039/d4cy00480a","url":null,"abstract":"<div><div>Lack of robust catalyst design strategies for tackling the selectivity and activity challenges poses serious limitations in the development of efficient catalysts for nitrogen reduction to ammonia. The synergistic interactions in double-atom catalysts (DACs) have aroused great interest in developing promising catalytic centers for the nitrogen reduction reaction (NRR). Using a multistep screening strategy based on systematic first-principles simulations, we find that Fe₂, Co₂, and W₂ dimer species impregnated in a tetracyanoquinodimethane-based monolayer achieve suitable adsorption behaviour for the various NRR intermediates, leading to excellent activity and selectivity among the 27 DACs considered in this study for the NRR. Interestingly, our results reveal very low limiting potential values of −0.56, −0.58, and −0.53 V for Fe₂, Co₂, and W₂, respectively, compared to the experimentally reported values of −0.73 and −0.98 V for the Ru-based single-atom catalyst and Ru(0001) stepped surface. Density of states analysis indicated that the adsorption pattern of the reaction intermediates was regulated by the d-states of the DACs near the Fermi level. Correlation trends between the limiting potential and the free energy change for adsorption of different intermediates show that the free energy change for N₂ adsorption proves a suitable guidance to evaluate the NRR activity of the modelled catalysts. Further, rigorous electronic structure analysis highlighted properties such as integrated crystal orbital Hamilton populations and orbital projected density of states, and the d-band centre could be successfully used to rationalize the N₂ binding and adsorption on these catalysts. Thus, this work provides a feasible design strategy for NRR electrocatalysis based on extensive electronic structure concepts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5687-5698"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329375","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":"Carbon-supported Zn-HPW ligand catalysts for acetylene hydration†","authors":"Zhen Chen ,&nbsp;Dingjie Luo ,&nbsp;Qinqin Wang ,&nbsp;Long Zhou ,&nbsp;Yufan Ma ,&nbsp;Fangjie Lu ,&nbsp;Bin Dai","doi":"10.1039/d4cy00806e","DOIUrl":"10.1039/d4cy00806e","url":null,"abstract":"<div><div>In recent years, the production of acetaldehyde with rich raw materials still has high research value. A series of Zn-HPW/AC catalysts with a Zn–O₄ configuration were prepared to solve the problems of easy loss of active components and carbon accumulation of Zn-based catalysts in the reaction. The characterization results showed that the phosphotungstic acid (HPW) ligands effectively promoted Zn species dispersion, provided more acid sites, mitigated the loss of Zn, and improved the carbon deposition resistance of the catalyst. The density functional theory (DFT) calculation further confirmed that the water molecules preferentially adsorb on the surface of the catalyst to promote the dissociation of water molecules, and the H of dissociation from water molecules and Zn forms the most stable Zn–OH configuration, which is the main active center of the reaction. Meanwhile the –OH dissociated from water molecules is adducted with C₂H₂, while H reduces the catalyst, and the original H atoms in the ligand catalyst further participate in the reaction to realize the catalytic cycle. This provides a new idea for the development of green catalysts for acetylene hydration.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5739-5745"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205498","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":"First principles investigation of manganese catalyst structure and coordination in the p-xylene oxidation process†","authors":"Harry N. Thomas ,&nbsp;Duncan F. Wass ,&nbsp;Caroline A. Offiler ,&nbsp;Keith Whiston ,&nbsp;Andrew J. Logsdail","doi":"10.1039/d4cy00284a","DOIUrl":"10.1039/d4cy00284a","url":null,"abstract":"<div><div>The oxidation of <em>p</em>-xylene to terephtalic acid has global importance, with the product used as a precursor for polyethylene terephthalate (PET). The oxidation of <em>p</em>-xylene proceeds <em>via</em> a redox cascade that involves cobalt, manganese, and bromide, with a synergy allowing for high selectivity and reactivity; however, the equilibrium coordination environment of the catalyst species remains uncertain due to the hostile industrial operating conditions. To build knowledge of the catalyst speciation and develop understanding of the reaction process, a density functional theory approach is applied herein to determine the static and dynamic properties of the divalent (reduced) and trivalent (oxidized) manganese catalysts in the redox cascade. The Gibbs free energy has been calculated for manganese as a function of ligands in the inner coordination sphere, with the octahedrally-coordinated Mn(OAc)₂(HOAc)₂ and Mn(OAc)₃(H₂O)₁ identified as the most thermodynamically stable coordination environments for Mn(<span>ii</span>) and Mn(<span>iii</span>), respectively. Dynamic properties of these catalysts in the presence of an explicit solvent environment have been determined using first principles molecular dynamics simulations. The simulations indicate 0–2 coordinating water ligands are present in the inner coordination sphere under standard industrial temperatures and pressures. The dynamical simulations have been extended to include HBr, which couples with Mn in the redox cascade, and the bromide species does not enter in the inner-coordination sphere of the oxidized Mn(<span>iii</span>) catalyst, providing evidence that the electron transfer between bromide and Mn(<span>iii</span>) proceeds <em>via</em> an outer sphere mechanism. Our results suggest that oxidation of Mn(<span>ii</span>) has the potential for facilitating L-type ligand exchange in the inner-sphere coordination environment. The results are a platform for developing a more complete knowledge of the reaction mechanism at the atomistic scale.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5634-5643"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00284a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226334","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":"Generating knowledge graphs through text mining of catalysis research related literature†","authors":"Alexander S. Behr ,&nbsp;Diana Chernenko ,&nbsp;Dominik Koßmann ,&nbsp;Arjun Neyyathala ,&nbsp;Schirin Hanf ,&nbsp;Stephan A. Schunk ,&nbsp;Norbert Kockmann","doi":"10.1039/d4cy00369a","DOIUrl":"10.1039/d4cy00369a","url":null,"abstract":"<div><div>Structured research data management in catalysis is crucial, especially for large amounts of data, and should be guided by FAIR principles for easy access and compatibility of data. Ontologies help to organize knowledge in a structured and FAIR way. The increasing numbers of scientific publications call for automated methods to preselect and access the desired knowledge while minimizing the effort to search for relevant publications. While ontology learning can be used to create structured knowledge graphs, named entity recognition allows detection and categorization of important information in text. This work combines ontology learning and named entity recognition for automated extraction of key data from publications and organization of the implicit knowledge in a machine- and user-readable knowledge graph and data. CatalysisIE is a pre-trained model for such information extraction for catalysis research. This model is used and extended in this work based on a new data set, increasing the precision and recall of the model with regard to the data set. Validation of the presented workflow is presented on two datasets regarding catalysis research. Preformulated SPARQL-queries are provided to show the usability and applicability of the resulting knowledge graph for researchers.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5699-5713"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00369a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329376","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":"Construction of visible light active CuS/MoS2 heterojunctions for heightened photoreduction of Cr(vi)","authors":"Aijing Ma ,&nbsp;Zaitian Tan ,&nbsp;Wenjie Liu ,&nbsp;Xueqian Li ,&nbsp;Kaibo Wang ,&nbsp;Yiming Zhang ,&nbsp;Xuan Jiao ,&nbsp;Jiahao Li ,&nbsp;Yuanyuan Yang ,&nbsp;Feiyan Fu","doi":"10.1039/d4cy00598h","DOIUrl":"10.1039/d4cy00598h","url":null,"abstract":"<div><div>CuS/MoS₂ heterojunctions were fabricated by a facile one-step hydrothermal method and evaluated <em>via</em> the photoreduction of Cr(<span>vi</span>) under visible light irradiation. The CuS/MoS₂ heterojunctions demonstrated a hierarchical porous structure, self-assembled from intersecting thin nanosheets, which resulted in a flower-like morphology. The optimized CuS/MoS₂ heterojunction (CuS/MoS₂-4.6) exhibited superior photocatalytic performance toward the removal of Cr(<span>vi</span>) under visible light with a <em>k</em> value of 1.33 × 10⁻² min⁻¹, which was much higher than that of pure CuS (2.13 × 10⁻⁴ min⁻¹) and MoS₂ (4.39 × 10⁻⁴ min⁻¹). The enhanced Cr(<span>vi</span>) photoreduction performance was ascribed to the construction of a type II CuS/MoS₂ heterojunction, in which electrons in the conduction band (CB) of CuS were transferred to the CB of MoS₂ due to the favorable band alignment, while holes in the valence band (VB) of MoS₂ flowed to the VB of CuS. This led to the efficient spatial separation and transfer of electrons and holes, inhibiting the recombination of photogenerated carriers, thus boosting the remarkable photocatalytic activity. This work provides a prospective heterojunction catalyst for photoreduction of Cr(<span>vi</span>).</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5746-5754"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205469","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":"Co(iii) corroles with pendant amidophenol and amidopyridine as proton-relay arms to facilitate the electrocatalytic hydrogen evolution reaction†","authors":"Xu-You Cao ,&nbsp;Shi-Yin Xu ,&nbsp;Ling-Wei Wu ,&nbsp;Yi-Feng Qiu ,&nbsp;Hao Zhang ,&nbsp;Li-Ping Si ,&nbsp;Li-Ming Wang ,&nbsp;Hai-Yang Liu","doi":"10.1039/d4cy00677a","DOIUrl":"10.1039/d4cy00677a","url":null,"abstract":"<div><div>It is known that the efficiency of the hydrogen evolution reaction (HER) can be promoted by the presence of proton relay groups neighboring a catalytic metal center. This work reports the synthesis of two new Co(<span>iii</span>) corroles (<strong>2</strong> and <strong>3</strong>) with hangman proton relay groups for the electrocatalytic HER. When using trifluoroacetic acid (TFA) as a proton source, complexes <strong>2</strong> and <strong>3</strong> exhibited turnover frequencies (TOFs) of 219.36 s⁻¹ and 199.57 s⁻¹, respectively. The catalytic HER undergoes <em>via</em> the EECEC or EECC pathway (E: electron transfer; C: charge transfer) depending on the acidity and concentration of the proton source. Moreover, complex <strong>2</strong> and <strong>3</strong> also showed good HER activity in aqueous media with Faraday efficiencies (FEs) of 93.6% and 89.2% respectively.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5608-5615"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329361","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 efficient cobalt catalysts promoted by CeO2–Al2O3 for ammonia decomposition†","authors":"Kai Xu ,&nbsp;Na Jiang ,&nbsp;Peng Wang ,&nbsp;Wei-Wei Wang ,&nbsp;Chun-Jiang Jia","doi":"10.1039/d4cy00835a","DOIUrl":"10.1039/d4cy00835a","url":null,"abstract":"<div><div>Hydrogen production by ammonia decomposition reveals great advantages in the utilization of hydrogen. Low-cost, efficient and stable transition metal catalysts are the key for the ammonia decomposition reaction. Using multi-component promoters adjust the electronic and geometric structures of bulk catalysts, which might be an effective approach for obtaining non-noble metal catalysts with excellent performance. In this work, CeO₂–Al₂O₃ bi-promoters were used and significantly improved the catalytic performance of bulk cobalt catalysts. The optimized CoCeAlO_x catalyst achieved 94.3% and 65.3% NH₃ conversion at 550 °C and 500 °C (GHSV = 30 000 mL g_cat⁻¹ h⁻¹), respectively, and exhibited strong stability within 200 h. It was found that the interaction between Co–CeO₂–Al₂O₃ effectively inhibited the aggregation of the Co⁰ active species, which enormously promoted the catalytic activity and stability of CoCeAlO_x. CeO₂–Al₂O₃ bi-promoters adjusted the surface properties of catalysts, bringing suitable NH₃ adsorption and N₂ desorption, and suppressing the hydrogen poisoning significantly. This work provided a reliable strategy for the construction of high-efficiency catalysts working under the harsh conditions for ammonia decomposition.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5678-5686"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329374","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":"Unraveling the impact of Ag dopant in Zn–In–S colloidal nanocrystals for boosting visible-light-driven photocatalytic CO2 reduction†","authors":"Jing Wang ,&nbsp;Shenshen Ouyang ,&nbsp;Ye Wang ,&nbsp;Xusheng Wang ,&nbsp;Xiaohui Ren ,&nbsp;Li Shi","doi":"10.1039/d4cy00716f","DOIUrl":"10.1039/d4cy00716f","url":null,"abstract":"<div><div>The development of durable and effective photocatalysts is significant for realizing efficient photocatalytic CO₂ conversion. In this work, heteroatom doped Zn–In–S colloidal nanocrystals are fabricated <em>via</em> a facile method, which can be utilized for photocatalytic CO₂ reduction under visible light in the presence of triethanolamine. Among various dopants, Ag shows the most effectiveness for improving the photocatalytic CO₂ reduction performance of Zn–In–S colloidal nanocrystals. The optimized Ag doped Zn–In–S colloidal nanocrystals with doping amount of 1.13 wt% exhibit the highest photocatalytic CO₂ reduction performance with a CO evolution rate of 30.29 μmol h⁻¹, achieving high selectivity of 96.06%. The photocatalytic mechanism study indicates that increasing the doping amount of Ag in Zn–In–S colloidal crystals would result in the improved visible light harvesting ability, increased charge carrier lifetime and weakened reduction potential of electrons, which exert a synergistic effect on the CO₂ photoreduction.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5616-5623"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205533","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":"Morphology dependence of Nb2O5-supported cobalt oxide in catalytic toluene oxidation†","authors":"Shuangju Li ,&nbsp;Xueli Cheng ,&nbsp;Wei Zhou ,&nbsp;Junxiang Jiang ,&nbsp;Chao Feng ,&nbsp;Yuanshuai Liu ,&nbsp;Xuebing Li ,&nbsp;Xiaodong Zhang ,&nbsp;Zhong Wang","doi":"10.1039/d4cy00596a","DOIUrl":"10.1039/d4cy00596a","url":null,"abstract":"<div><div>This research describes the preparation of cobalt-based catalysts supported on Nb₂O₅ substrates of various forms: rods (Nb₂O₅-R), grids (Nb₂O₅-G), and spherical structures (Nb₂O₅-S). These catalysts demonstrated diverse reactivity in toluene oxidation, which correlated with their individual physical and chemical traits and the interfacial interaction between cobalt oxide and the Nb₂O₅ support. Notably, the catalyst with a spherical Nb₂O₅ support (CoO_x/Nb₂O₅-S) outperformed the catalysts with other supports and showed the best activity in oxidizing toluene. The investigation underscored the role of the unique features of the Nb₂O₅ substrate in augmenting the catalyst's efficacy in toluene adsorption and activation. Density functional theory (DFT) revealed more facile toluene adsorption on CoO_x/Nb₂O₅-S (−0.65 eV) and reduced energy requirements for oxygen vacancy creation and adsorption. This suggested that the CoO_x/Nb₂O₅-S catalyst enhanced surface oxygen mobility and boosted catalytic efficiency.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5722-5730"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205534","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":"Substrate-directed C(sp3)–H borylation via transition metal catalysis: expanding the toolbox for C–H functionalization","authors":"Dolly David Thalakottukara ,&nbsp;Manikandan Sekar ,&nbsp;Astam Mandal ,&nbsp;Thirumanavelan Gandhi ,&nbsp;Debabrata Maiti","doi":"10.1039/d4cy00754a","DOIUrl":"10.1039/d4cy00754a","url":null,"abstract":"<div><div>Organoborons play a crucial role in organic synthesis, easing the construction of C–C and C–X bonds, which in turn sensitize C–H borylation reactions. In the context of inert C(sp³)–H borylation, significant efforts have been dedicated to achieve site- and chemoselectivity by involving directing groups <em>via</em> transition metal catalysis. This review highlights various types of directing groups that can enable intricate and distal C(sp³)–H borylation; heteroatoms such as P, N, B, Si, Br, O, and Cl, which are attached to the substrate, act as the directing group. In addition to homogeneous catalysis, the occurrence of heterogeneous catalysis was realized, and the considerable contribution to chiral C(sp³)–H borylation is discussed. Finally, this review summarizes the mechanistic aspects and late-stage modifications of complex molecules.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 19","pages":"Pages 5488-5504"},"PeriodicalIF":4.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329320","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}