Applied Catalysis A: General最新文献

{"title":"Chlorobenzene Oxidation by Electrochemical Catalysis with La Modified Ti/IrO2-Ta2O5","authors":"Shicheng Yuan ,&nbsp;Zhongming Chen ,&nbsp;Jinxing Mi ,&nbsp;Pan Wang ,&nbsp;Jiaren Zheng ,&nbsp;Kunpeng Li ,&nbsp;Mi Zhang ,&nbsp;Fan Zeng ,&nbsp;Hui Hu ,&nbsp;Hao Huang","doi":"10.1016/j.apcata.2024.119865","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119865","url":null,"abstract":"<div><p>As a typical VOCs emitted from petrochemical industry, chlorobenzene was selected to study its removal by wet oxidation with electrochemical catalysis. Ti based IrO₂-Ta₂O₅ electrode was used in the advanced oxidation of chlorobenzene, and Sn, Sb, Pt and La were used to modify Ti/IrO₂-Ta₂O₅. Ti/IrO₂-Ta₂O₅-La showed the highest removal rate of chlorobenzene and it reached 99.2% for the chlorobenzene oxidation, which was 20% higher than those of the other 3 additions. Oxygen evolution overpotential of Ti/IrO₂-Ta₂O₅-La increased to 1.17<!--> <!-->V when compared with Ti/IrO₂-Ta₂O₅ of 1.08<!--> <!-->V. EPR tests for free radicals and GC-MS tests for intermediates showed that the main active substance was <strong>·</strong>OH, and the element Cl in chlorobenzene dissociated from the benzene ring under the action with <strong>·</strong>OH to form <strong>·</strong>Cl and ClO<strong>·</strong> radicals. Degradation pathway of chlorobenzene was figured out as chlorobenzene→ phenols→ organic acids→ CO₂+H₂O.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141605213","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pd-N-doped carbons for chemoselective hydrogenation of cinnamaldehyde: Unravelling the influence of particle size and support in multiphase batch and continuous-flow systems","authors":"","doi":"10.1016/j.apcata.2024.119864","DOIUrl":"10.1016/j.apcata.2024.119864","url":null,"abstract":"<div><p>The chemoselective hydrogenation of the C<img>C bond of cinnamaldehyde (CAL) was investigated under batch and continuous flow conditions, by comparing the performance of two <em>ad-hoc</em> prepared palladium-based catalysts supported on <em>N</em>-doped carbons to that of a commercial Pd/C system. An impregnation (I) and a solution-mediated (S) protocols were used for the synthesis of the catalytic materials, Pd-N/C_i and Pd-N/C_s, respectively, in the presence of chitin as a precursor of the support. The S method afforded palladium nanoparticles of 2.0±0.5 nm, while by impregnation, a wider size distribution was achieved with particles mostly belonging to two groups displaying a mean radius of 3.0±0.5 nm and 8.4±0.5 nm, respectively. A parametric analysis of the hydrogenation reaction showed that both the reaction conditions and the nature of the catalysts played a role to steer the selectivity towards the formation of the desired product, 3-phenylpropanal (hydrocinnamaldehyde, HCAL). At 50 °C and 1 bar H₂, in a triphasic (liquid-liquid-liquid) batch reactor where the catalyst was compartmentalized in an ionic liquid layer, Pd-N/C_i and commercial Pd/C were almost equally active and allowed to obtain HCAL in a 90–96 % selectivity at complete conversion. On the other hand, at the same T and p (50 °C/1 bar), Pd-N/C_s was more effective in the continuous-flow mode: the process was quantitative yielding HCAL with a selectivity and a productivity of 91 % of 16 mmol (g_cat h)⁻¹, respectively, while the catalyst proved highly stable showing no loss of activity over 300 min of time on-stream. The reaction environment, the size and dispersion of the metal active sites, and the nature of the catalyst support were major contributors to such results, acting synergistically to each other to tune the energetics of adsorption/desorption of reactants/products, of the interfacial interactions/ barriers, and in the last analysis, of the process kinetics/selectivity.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141729139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergy and site dependent kinetics of photo-thermal catalysis over Pt/TiO2 for methanol decomposition","authors":"Chenghao Yao ,&nbsp;Jinbiao Huang ,&nbsp;Can Yang ,&nbsp;Weiwei Deng ,&nbsp;Lei Li ,&nbsp;Zhan Lin","doi":"10.1016/j.apcata.2024.119862","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119862","url":null,"abstract":"<div><p>Photo-thermal catalysis which interplay the heat and light-induced effects have drawn broad attention owing to their synergistic effect to extend the capability of chemical transformation. Here, the effect of heat and/or light on methanol decomposition has been clarified. On Pt/TiO₂, light irradiation activates the TiO₂ and enhance the absorption and the oxidation of intermediates. The main intermediate under PTC condition is formaldehyde, which is the same to TC condition rather than methyl formate under PC condition. Differences CO absorption site correlates with the key intermediates under PC and TC/PTC conditions. Light and heat display their strengths in a synergistic manner, optimizing the activity to promote efficient catalytic processes which is verified to be photo-assisted thermal catalysis. This work offers detailed mechanistic understanding of the surface species and paves the way for an educated microkinetic modeling approach under photo and/or thermal condition over oxide-supported metal catalysts.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141539711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Fischer-Tropsch synthesis: Platinum promoted Co@HCS catalysts","authors":"","doi":"10.1016/j.apcata.2024.119863","DOIUrl":"10.1016/j.apcata.2024.119863","url":null,"abstract":"<div><p>Hollow carbon sphere (HCS) nanoreactors were used as a catalyst support for Co, with Pt as a promoter. The hollow morphology of the HCSs nanoreactor was exploited to study the influence of the Pt promoter nanoparticle location relative to that of the Co₃O₄ (Co 10 wt%) nanoparticles (d_Co = 3.5 – 12.5). Furthermore, the effect of Pt on the reduction behaviour and activity of the Co FTS catalyst was evaluated. The synthesis and use of Pt nanoparticles supported on/in Co@HCS FT catalysts to give CoPt@HCS and Pt/(Co@HCS) catalysts are reported. Electron microscopy, ex situ PXRD, BET, and TPR studies revealed that the prepared catalysts were successfully synthesized with well dispersed Co nanoparticles. It was observed that the proximity between the Co and Pt influenced the Co hcp/fcc ratios. A secondary hydrogen spillover effect was invoked to account for the reduction of Co₃O₄ on 1Pt/(10Co@HCS) at 335 °C. The complete reduction of Co₃O₄ to Co metal on 10Co1Pt@HCS at 350 °C was attributed to a primary hydrogen spillover effect. Following catalyst activation at 350 °C, the primary spillover process resulted in a catalyst exhibiting higher Fischer–Tropsch activity (approximately 2×) compared to both the unpromoted catalyst and catalysts where Pt and Co were separated by the HCS. This enhanced activity was partially attributed to the Co phases formed on the carbon support during reduction and the degree of catalyst reduction, which depended on the type of hydrogen spillover process. A comparison of the reduction ability of Os, Ru and Pt on the reduction of Co supported on/in HCSs and the impact of the promoter on Co hcp/fcc ratios is reported.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926860X24003089/pdfft?md5=ef4c01c30dda04d3a3a79b4e046d5569&pid=1-s2.0-S0926860X24003089-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141700177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Transformation of syngas to valuable oxygenated products over Rh-MnOx/SiO2, Rh-Co/ZrO2 and Rh-Cu/ZrO2 catalysts","authors":"Noora Lind,&nbsp;Atte Aho,&nbsp;Kari Eränen,&nbsp;Pasi Virtanen,&nbsp;Irina Simakova,&nbsp;Päivi Mäki-Arvela,&nbsp;Dmitry Yu. Murzin","doi":"10.1016/j.apcata.2024.119852","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119852","url":null,"abstract":"<div><p>The conversion of syngas into higher alcohols was examined using bimetallic Rh-Co, Rh-Cu, and multimetallic RhCuPd catalysts, all of which were supported on ZrO₂. This process was also studied using a MnOx-promoted Rh/SiO₂ catalyst. These experiments were conducted within a temperature range of 225–300 °C, under a pressure of 30 bar, and with a H₂/CO ratio of 2. The catalysts were characterized using a variety of physicochemical methods, including Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Carbon Monoxide Diffuse Reflectance Infrared Fourier Transform Spectroscopy (CO DRIFTS). The Rh particle sizes in the fresh catalysts were found to be less than 3 nm. The Rh-Co catalyst supported on ZrO₂ exhibited the highest selectivity to ethanol, achieving 38 % at a CO conversion rate of 58 % at 275 °C. This catalyst also demonstrated a chain growth probability of 0.35 for alcohols. A slightly higher chain growth probability was observed with the Rh-MnOx/SiO₂ catalyst, although this also resulted in the formation of substantial amounts of acetic acid. Interestingly, this acetic acid could be converted into ketones when RhMnOx was used in conjunction with Pd/ZrO₂.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926860X24002977/pdfft?md5=20526dd6c5ee211633ddaac9482f2cd1&pid=1-s2.0-S0926860X24002977-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141539710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Morphology and size modulation of Mn2O3 catalysts derived from MnBDC to enhance propane complete oxidation","authors":"Tao Peng ,&nbsp;Chuanqiang Li ,&nbsp;Liyun Song ,&nbsp;Cui Liu ,&nbsp;Feng Wang ,&nbsp;Qianqian Chai ,&nbsp;Shimin Li ,&nbsp;Qiang Guo ,&nbsp;Xuxu Zheng","doi":"10.1016/j.apcata.2024.119861","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119861","url":null,"abstract":"<div><p>Three Mn₂O₃ with different morphologies and particle sizes were synthesized using MnBDC as precursor. Interestingly, the morphology and size of MnBDC can be easily regulated by changing the reaction solvents slightly. The Mn₂O₃-L catalyst with large layers and small crystal size exhibited the best catalytic activity for complete oxidation of propane, with <em>T</em>₅₀ of 266℃ and T90 of 311℃ at the WHSV of 120 L g⁻¹ h⁻¹. The multi-layered structure and small crystal size of Mn₂O₃-L allowed it to possess a high surface area and more interfacial oxygen defects that facilitated oxygen mobility, improving the catalytic activity. It seems that the large precursor size of MnBDC-L slowed down the decomposition rate of ligands, promoting the formation of large layered structure and small crystal size of Mn₂O₃-L. This study offers a simple strategy to control the structure and crystal size of Mn₂O₃ catalysts.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141595334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photoelectrochemical catalytic CO2 reduction enhanced by In-doped GaN and combined with vibration energy harvester driving CO2 reduction","authors":"Mingxiang Zhang ,&nbsp;Wen Luo ,&nbsp;Shanghao Gu ,&nbsp;Weihan Xu ,&nbsp;Zhouguang Lu ,&nbsp;Fei Wang","doi":"10.1016/j.apcata.2024.119859","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119859","url":null,"abstract":"<div><p>Photoelectrochemical (PEC) technology seamlessly integrates and optimizes the merits of photocatalysis and electrocatalysis, facilitating charge separation and enhancing solar conversion efficiency. It stands out as a promising approach for CO₂ treatment. GaN as III-Ⅴ semiconductor, has garnered substantial attention in the realm of PEC CO₂ reduction reactions (RR). In this study, GaN and In/GaN micro-rods were prepared via straightforward hydrothermal synthesis. Attaining a current density of approximately 10 mA/cm² and CO Faradaic Efficiency (FE) of ∼45 % at −0.75 V_RHE (Reversible Hydrogen Electrode, RHE), In/GaN exhibited exceptional stability over a 2 h PEC CO₂ RR. The introduction of In into GaN significantly augmented CO₂ adsorption capacity and light harvesting. Additionally, Density Functional Theory (DFT) calculations elucidated that In-doped GaN can diminish the adsorption of intermediate CO, favoring subsequent CO desorption. Furthermore, the N-vacancy increased with In doping, resulting in a rise in the number of unpaired electrons, facilitating carrier transport. Herein, vibration energy harvester was introduced to drive CO₂ RR, marking a significant advancement in development of PEC CO₂ RR for future green energy applications.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141486841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of pretreatment conditions on a benchmark iron catalyst for CO2 hydrogenation to light olefins","authors":"E. Kraleva ,&nbsp;H. Lund ,&nbsp;J. Weiß ,&nbsp;S. Bartling ,&nbsp;H. Atia ,&nbsp;Z. Cherkezova-Zheleva ,&nbsp;D. Paneva ,&nbsp;S. Wohlrab ,&nbsp;U. Armbruster","doi":"10.1016/j.apcata.2024.119857","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119857","url":null,"abstract":"<div><p>To improve the CO₂-to-light olefin process in terms of economics, efficient catalysts are essential to maximize the yield. Our research was carried out on FeAlCuK, which is still considered as a benchmark for olefin formation via CO₂ Fischer-Tropsch synthesis (FTS). Nevertheless, the effect of various activation conditions on the formation of desired active species and final activity of this catalyst has not been described in literature to date. We studied the pretreatment by varying both the reduction gas and temperature. The catalyst was pretreated with pure H₂ or synthesis gas (H₂/CO = 3) to identify the bulk and surface species formed in each case. We demonstrate that the FeCuAlK catalyst should be activated in a H₂/CO atmosphere at 250 °C for 4 h before the test at typical FTS reaction conditions to reach maximum productivity. The reduction with H₂/CO led to the formation of active Fe₅C₂ and Fe₃O₄ phases producing a high fraction of light olefins at higher CO₂ conversion. The role of promoters K and Cu was also investigated. Selectivity for desired C₂-C₄ olefins increased by 10 % compared to catalysts which were used directly in FTS without preliminary activation. Characterization with <em>ex</em> and <em>in situ</em> powder X-ray diffraction, Raman spectroscopy, and XPS after each activation treatment as well as Mössbauer spectroscopy revealed a strong impact of gas nature on the phase composition which was correlated with the performance.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141486839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Raney nickel induced interface modulation of active NiFe-hydroxide as efficient and robust electrocatalyst towards oxygen evolution reaction","authors":"Yaqi Mao ,&nbsp;Kai Zhang ,&nbsp;Shuaichong Wei ,&nbsp;Jingde Li ,&nbsp;He Xiao ,&nbsp;Guihua Liu","doi":"10.1016/j.apcata.2024.119858","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119858","url":null,"abstract":"<div><p>Preparation of active and durable low-cost catalysts towards oxygen evolution reaction (OER) is essential for alkaline water splitting. Herein, porous Raney-Ni supported NiFe-LDH (NiFe-LDH/Raney-Ni) electrocatalyst was developed to achieve efficient and robust OER performance. Raney-Ni modulates the NiFe-LDH electronic structure by interfacial interaction. <em>In-situ</em> infrared shows the enhanced OH adsorption behavior, and <em>in-situ</em> Raman suggests that Raney-Ni promotes the formation of active NiFeOOH species on NiFe-LDH/Raney-Ni. Theoretical calculations found that the Fe atoms in NiFe-LDH/Raney-Ni enhances the charge transfer to the NiOOH species, which facilitates the formation of O* intermediates accelerating the OER process. The NiFe-LDH/Raney-Ni catalyst exhibits a low OER overpotential of 219 mV at 10 mA cm⁻² in 1 M KOH with excellent stability for 200 h at 200 mA cm⁻². Excellent performance is also achieved in alkaline electrolyzer test. This work presents a facile approach for the design of affordable and efficient alkaline OER electrocatalysts.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141540516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A green and moderate approach for the synthesis of methyl formate via dimethoxymethane disproportionation over H-zeolites","authors":"Leilei Yang ,&nbsp;Youming Ni ,&nbsp;Mingguan Xie ,&nbsp;Zhiyang Chen ,&nbsp;Xudong Fang ,&nbsp;Bin Li ,&nbsp;Hongchao Liu ,&nbsp;Wenliang Zhu","doi":"10.1016/j.apcata.2024.119860","DOIUrl":"https://doi.org/10.1016/j.apcata.2024.119860","url":null,"abstract":"<div><p>Methyl formate (MF) is an important building block in the modern chemical industry, primarily produced through homogeneous carbonylation of methanol under harsh reaction conditions. It is of great interest but remains challenges to develop new heterogeneous catalytic system under mild reaction conditions to replace the homogeneous route. Herein, we report an efficient and green strategy for MF production by dimethoxymethane (DMM) disproportionation over acidic zeolites. Up to nearly100 % DMM conversion and 0.76 g g_cat⁻¹ h⁻¹ of MF space time yield (STY) is achieved over H-SSZ-13 under moderate conditions of 0.1 MPa and 393 K. Moreover, H-SSZ-13 shows superior stability during a 100 h continuous test. Combined with multiple characterizations, formaldehyde (FA) has been proved to be a crucial precursor for the formation of MF and the complete mechanism is proposed. This strategy provides a new and feasible approach for continuous large-scale MF production using acidic zeolite as catalyst by heterogeneous catalytic systems.</p></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":null,"pages":null},"PeriodicalIF":4.7,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141540519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}