Catalysis Science & Technology最新文献

{"title":"Defective TiO2 composite photoanodes with surface-modified Prussian blue for efficient photoelectrochemical water splitting","authors":"Lipeng Wang, Rui Wang, Longjie Lai, Waqar Younas, Guobing Mao, Li Zhang, Qi Liu","doi":"10.1039/d4cy00895b","DOIUrl":"https://doi.org/10.1039/d4cy00895b","url":null,"abstract":"Solar hydrogen production has garnered significant attention in addressing the energy crisis due to its efficient and environmentally friendly nature. In this study, we successfully used a simple electrochemical reduction method to introduce oxygen vacancies on a TiO<small>₂</small> nanorod photoanode, termed defective TiO<small>₂</small> (D-TiO<small>₂</small>). Meanwhile, Prussian blue (PB) was deposited on D-TiO<small>₂</small> to create a core–shell composite photoanode material. By optimizing the reduction time, the charge separation of D-TiO<small>₂</small> is improved. The addition of PB resulted in the formation of a II-type heterojunction between TiO<small>₂</small> and PB. The formation of the heterojunction enlarges the light absorption range of TiO<small>₂</small>, increases the active sites, and reduces the recombination of photogenerated charges due to the large surface area of PB. The photocurrent density of D-TiO<small>₂</small>@PB reaches 2.10 mA cm<small>⁻²</small> at 1.23 V <em>vs.</em> RHE, with an enhanced IPCE of 35.8%.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205526","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":"Electrochemically synthesized Ce-doped Cu-mesh catalyst with high activity and stability towards HMF to FDCA conversion†","authors":"Haoran Wu, Qi Liu, Didi Li, Haoyuan Gu, Hao Liu, Xiaohui Liu, Zixu Yang, Jing Xu and Minghui Zhu","doi":"10.1039/D4CY00851K","DOIUrl":"10.1039/D4CY00851K","url":null,"abstract":"<p >The electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to high value-added downstream products is a sustainable and cost-effective strategy. In this study, a series of copper-based HMF oxidation reaction (HMFOR) catalysts were synthesized through a modified chronopotentiometry method using copper mesh as a starting material. The cerium-doped copper mesh catalyst, denoted as Ec CM-Ce demonstrates exceptional performance in the HMFOR, exhibiting remarkable selectivity (99.2%), yield (96.4%), Faraday efficiency (92.6%), and stability (12 cycles without significant activity decay). X-ray diffraction and surface-enhanced <em>in situ</em> Raman spectroscopy demonstrated the transformation of Cu<small>₂</small>O to CuO during the oxidation of HMF to FDCA. Electrochemical impedance spectroscopy and surface-enhanced <em>in situ</em> infrared spectroscopy indicated that cerium enhanced the electron transfer efficiency and adsorption of water as well as organic molecules. This study not only introduces a novel method for synthesizing electro-catalysts but also suggests innovative approaches for the electrochemical HMF oxidation.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205537","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, Duncan F. Wass, Caroline A. Offiler, Keith Whiston, Andrew J. Logsdail","doi":"10.1039/d4cy00284a","DOIUrl":"https://doi.org/10.1039/d4cy00284a","url":null,"abstract":"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)<small>₂</small>(HOAc)<small>₂</small> and Mn(OAc)<small>₃</small>(H<small>₂</small>O)<small>₁</small> identified as the most thermodynamically stable coordination environments for Mn(<small>II</small>) and Mn(<small>III</small>), 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(<small>III</small>) catalyst, providing evidence that the electron transfer between bromide and Mn(<small>III</small>) proceeds <em>via</em> an outer sphere mechanism. Our results suggest that oxidation of Mn(<small>II</small>) 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.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning catalytic performance of platinum single atoms by choosing the shape of cerium dioxide supports.","authors":"Petrus C M Laan, Martijn J Mekkering, Felix J de Zwart, Alessandro Troglia, Roland Bliem, Kai Zhao, Norbert J Geels, Bas de Bruin, Gadi Rothenberg, Joost N H Reek, Ning Yan","doi":"10.1039/d4cy00484a","DOIUrl":"10.1039/d4cy00484a","url":null,"abstract":"<p><p>The local coordination environment of single atom catalysts (SACs) often determines their catalytic performance. To understand these metal-support interactions, we prepared Pt SACs on cerium dioxide (CeO₂) cubes, octahedra and rods, with well-structured exposed crystal facets. The CeO₂ crystals were characterized by SEM, TEM, pXRD, and N₂ sorption, confirming the shape-selective synthesis, identical bulk structure, and variations in specific surface area, respectively. EPR, XPS, TEM and XANES measurements showed differences in the oxygen vacancy density following the trend rods > octahedra > cubes. AC-HAADF-STEM, XPS and CO-DRIFTS measurements confirmed the presence of only single Pt²⁺ sites, with different surface platinum surface concentrations. We then compared the performance of the three catalysts in ammonia borane hydrolysis. Precise monitoring of reaction kinetics between 30-80 °C gave Arrhenius plots with hundreds of data points. All plots showed a clear inflection point, the temperature of which (rods > octahedra > cubes) correlates to the energy barrier of ammonia borane diffusion to the Pt sites. These activity differences reflect variations in the - facet dependent - degree of stabilization of intermediates by surface oxygen lone pairs and surface-metal binding strength. Our results show how choosing the right macroscopic support shape can give control over single atom catalysed reactions on the microscopic scale.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11322700/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141998941","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":"Retraction: In situ construction of S-scheme heterojunction-conjugated polymer/g-C3N4 photocatalysts for enhanced H2 production and organic pollutant degradation","authors":"Na Mao","doi":"10.1039/D4CY90073A","DOIUrl":"https://doi.org/10.1039/D4CY90073A","url":null,"abstract":"<p >Retraction of ‘<em>In situ</em> construction of S-scheme heterojunction-conjugated polymer/g-C<small>₃</small>N<small>₄</small> photocatalysts for enhanced H<small>₂</small> production and organic pollutant degradation’ by Na Mao, <em>Catal. Sci. Technol.</em>, 2023, <strong>13</strong>, 4197–4206, https://doi.org/10.1039/D3CY00248A.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy90073a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142077713","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 error imbalance of large-scale machine learning potentials in catalysis","authors":"Kareem Abdelmaqsoud, Muhammed Shuaibi, Adeesh Kolluru, Raffaele Cheula, John R. Kitchin","doi":"10.1039/d4cy00615a","DOIUrl":"https://doi.org/10.1039/d4cy00615a","url":null,"abstract":"Machine learning potentials (MLPs) have greatly accelerated atomistic simulations for material discovery. The Open Catalyst 2020 (OC20) dataset is one of the largest datasets for training MLPs for heterogeneous catalysis. The mean absolute errors (MAE) of the MLPs on the energy target of the dataset have asymptotically approached about 0.2 eV over the past two years with increasingly sophisticated models. The errors were found to be imbalanced between the different material classes with non-metals having the highest errors. In this work, we investigate several potential sources for the imbalanced distribution of errors. We examined material class-specific convergence errors in the density functional theory (DFT) calculations including <em>k</em>-point sampling, plane wave cutoff and smearing width. Significant DFT convergence errors with a mean absolute value of ∼0.15 eV were found on the total energies of non-metals, higher than the other material classes. However, as a result of cancellation of errors, convergence errors on adsorption energies have a mean absolute value of ∼0.05 eV across all material classes. Moreover, we found that the MAEs of the MLPs are not affected by these convergence errors. Second, we show that calculations with surface reconstruction can introduce inconsistencies to the adsorption energy referencing scheme that cannot be fit by the MLPs. Nonmetals and halides were found to have the highest fraction of calculations with surface reconstructions. Removing calculations with surface reconstructions from the validation sets, without re-training, significantly lowers the MAEs by ∼35% and reduces the imbalance of the MAEs. Alternatively, MLPs trained on total energies provide a solution to the surface reconstruction inconsistencies since they eliminate the referencing issue, and have comparable MAEs to MLPs trained on adsorption energies.","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205532","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":"Effect of N-heterocyclic carbene in palladium–tin heterobimetallic catalysis: a DFT supported study on the C3–H functionalization of unprotected indoles†","authors":"","doi":"10.1039/d4cy00224e","DOIUrl":"10.1039/d4cy00224e","url":null,"abstract":"<div><p>A new N-heterocyclic carbene (NHC)-based Pd–Sn heterobimetallic complex [(NHC)Pd(μ-Br)SnCl₃]₂ with low steric crowding in the active catalytic region was designed. The reactivity of this complex was compared with a previously reported NHC–Pd–Sn complex (NHC)₂PdBrSnCl₃ towards the C3–H functionalization of indoles with styrenes. The role of NHC in heterobimetallic catalysis was investigated in terms of the density functional theory by comparing the reactivity of these catalysts along with a cyclooctadiene (COD)-based Pd–Sn catalyst (COD)PdClSnCl₃. Thermochemical calculations revealed that the catalytic cycle is thermodynamically favorable in the case of the NHC-based catalysts but not in the case of the COD-based one. An inverse kinetic isotope effect with a <em>k</em>_H/<em>k</em>_D of 0.44 was detected. This alludes to the migration of a hydride from the metal center to the carbon center being the rate-determining step of the reaction. Based on the experimental and computational findings, an appropriate mechanism is proposed.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141718054","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":"Catalytic dehalogenation with activated borane, a porous borane cluster polymer†","authors":"","doi":"10.1039/d4cy00732h","DOIUrl":"10.1039/d4cy00732h","url":null,"abstract":"<div><p>Activated borane (<strong>ActB</strong>), a metal- and halogen-free porous borane cluster polymer with a significant Lewis acidity, has been successfully used as a heterogeneous catalyst for hydrodehalogenation reactions of aliphatic fluorides and chlorides using triethylsilane as a reductant. In analogy to known homogeneous systems, full dehalogenation of organohalides is achieved with a predominant formation of Friedel–Crafts alkylation products in aromatic reaction media. Importantly, the herein described material is robust, tolerates elevated reaction temperatures and can be re-used, while reaching a turnover number (TON) of up to 5190. These features make it an attractive candidate for a sustainable disposal of halogenated pollutants by heterogeneous catalysis.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00732h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141771056","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":"2,3-Diamino-4,5-diarylcyclopentadienone iron carbonyl complexes as catalysts for reductive amination reactions†","authors":"","doi":"10.1039/d4cy00372a","DOIUrl":"10.1039/d4cy00372a","url":null,"abstract":"<div><p>The reaction of dipiperidinoacetylene, (CH₂)₅NCCN(CH₂)₅, with a series of 2,3-diarylcyclopropenones (Ar)₂C₃O (Ar = phenyl, 4-<em>tert</em>-butylphenyl, 2,5-dimethylphenyl, 4-trifluoromethylphenyl) afforded 2,3-dipiperidino-4,5-diarylcyclopentadienones, which were used to prepare cyclopentadienone (CPD) iron tricarbonyl complexes [(CPD)Fe(CO)₃] by the reaction with Fe₂(CO)₉. Subsequent treatment with trimethylamine-<em>N</em>-oxide in the presence of acetonitrile afforded the corresponding acetonitrile complexes [(CPD)Fe(CO)₂(NCCH₃)], which were used as catalysts for the reductive amination of citronellal with various secondary amines under 5 bar of dihydrogen pressure. The first iron-catalysed reductive amination for the preparation of the pharmaceutically important antidepressant sertraline is also reported.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00372a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141611415","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":"Catalytic processes for the selective hydrogenation of fats and oils: reevaluating a mature technology for feedstock diversification","authors":"","doi":"10.1039/d4cy00488d","DOIUrl":"10.1039/d4cy00488d","url":null,"abstract":"<div><p>The selective hydrogenation of polyunsaturated fatty acids (PUFAs) and their derivatives to their monounsaturated counterparts is a critical catalytic step in various disciplines, such as biofuels and food chemistry. Furthermore, the necessary transformation of the chemical industry towards sustainability and circularity demands the development of new platform chemicals from renewable resources. The selective hydrogenation of PUFAs offers the flexibility to use a variety of commodity feedstocks in existing processes in the chemical value chain; this is indispensable for staying competitive and in shaping a sustainable future-proof chemical industry. The naturally occurring differences in the composition of vegetable fats and oils, especially the degree of saturation of the carbon chain, necessitate a preparation step to provide a standardized feedstock for existing chemical processes. Since many chemical reactions towards valuable intermediates start from mono-unsaturated substrates, selectivity plays a crucial role in hydrogenation. Furthermore, standardization alleviates the need to grow speciality monocultures or to utilize edible substrates, to further reducing the negative impact on society and the environment. In this critical review, all the relevant and pioneering catalytic transformations throughout history up to this time and place are discussed and evaluated towards their applicability and usefulness for the provision of renewable-based resources for the chemical industry, with particular emphasis on the selectivity towards mono-unsaturated substrates.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00488d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141502543","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}