{"title":"Regulating the location relationship between Cu nanoparticles and Pt atoms to enhance the catalytic hydroisomerization performance: Together or apart?","authors":"Hao Qin, Hui Wan, Guofeng Guan","doi":"10.1016/j.mcat.2024.114620","DOIUrl":"10.1016/j.mcat.2024.114620","url":null,"abstract":"<div><div>Single atom catalysts have been recently reported as the efficient catalysts for hydroisomerization compared to the conventional nanoparticle catalyst. Despite the fascinating advantage in enhancing the metal activity or reducing the catalyst cost, the long-term stability of the single atom catalyst seemed not that satisfactory, especially when reacting under atmospheric pressure. Herein, Pt single atom catalysts were combined with Cu nanoparticles by different means to explore a new way to improve the catalytic performance. Cu nanoparticles were located away from Pt sites to form a binary catalyst, or acted as the support of Pt atoms to form a single atom alloy (SAA) catalyst. With the binary catalyst Pt<sub>1</sub>–0.1Cu@CS, the conversion of the <em>n</em>-heptane after time on stream of 50 h increased to 70.3 %, higher than Pt<sub>1</sub>@CS (47.3 %). Besides, excessive Cu nanoparticles in the binary catalyst were found rather harmful to the catalysis instead. However, the SAA catalyst Pt<sub>1</sub>Cu@SAPO-11 showed a poor activity in hydroisomerization compared to Pt<sub>1</sub>@CS, indicating that the alloy structure should go against the activation of reactant. The roles of Pt atoms and Cu nanoparticles in different catalysts were discussed in detail. The reaction mechanism of hydroisomerization was refined with the different functions of the dual metal sites. This work might be instructive for the design of single atom catalysts combined with metal nanoparticles.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114620"},"PeriodicalIF":3.9,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446443","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}
Dezhou Luo , Na Zhang , Chunying Chen , Zhi Chen , Sisi Qin , Qin He , Zhengzheng Yang
{"title":"Engineering the structure defects of ceria-zirconia-praseodymia solid solutions for diesel soot catalytic elimination","authors":"Dezhou Luo , Na Zhang , Chunying Chen , Zhi Chen , Sisi Qin , Qin He , Zhengzheng Yang","doi":"10.1016/j.mcat.2024.114623","DOIUrl":"10.1016/j.mcat.2024.114623","url":null,"abstract":"<div><div>Creating structure defects in ceria-based solid solution catalysts is a crucial yet challenging task. Herein, urea-assisted synthesis strategy was designed for ceria-zirconia-praseodymia catalyst (CeZrPrO<sub>x</sub>) to create lattice defects; its effects on catalyst structure, physical-chemical properties and catalytic diesel soot purification activity were systematically investigated. Raman and X-ray photoelectron spectroscopy (XPS) findings indicate that the urea-assisted synthesized catalyst (CeZrPrO<sub>x</sub>-U) has remarkably more Ce<sup>3+</sup> proportion (structure defects), oxygen vacancies and surface reactive oxygen species (O<sub>2</sub><sup>2-</sup> and O<sup>2-</sup>). Temperature-programmed reduction by hydrogen (H<sub>2</sub>-TPR) and temperature-programmed desorption by oxygen (O<sub>2</sub>-TPD) results further prove that the oxygen migration of the CeZrPrO<sub>x</sub>-U is definitely enhanced. Compared to the conventional CeZrPrO<sub>x</sub> catalyst, the bulk lattice oxygen of the CeZrPrO<sub>x</sub>-U can be migrated to the surface to generate surface reactive oxygen species more easily. As a consequence, the prepared CeZrPrO<sub>x</sub>-U catalyst exhibits obviously better catalytic diesel soot purification activity. Therefore, this study suggests that engineering the structure defects in CeZrPrO<sub>x</sub> catalyst is an effective approach to improve physical-chemical properties and enhance the soot catalytic elimination activity of the catalyst.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142442085","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":"What size of Cun clusters loaded on poly(heptazine imide) have better catalytic performance for acetylene semi-hydrogenation?","authors":"Xiaoxiao Chen , Yi Li , Yaofeng Yuan , Wei Lin","doi":"10.1016/j.mcat.2024.114605","DOIUrl":"10.1016/j.mcat.2024.114605","url":null,"abstract":"<div><div>Development of earth-abundant, low-cost and easily synthesizable catalysts for the semi-hydrogenation of acetylene is urgently needed. Here, we have systematically investigated the structure, electronic properties, hydrogen dissociation, and acetylene semi-hydrogenation activity and selectivity of poly(heptazine imide) (PHI) loaded with different sizes of Cu<sub>n</sub> (<em>n</em> = 1,2,4,13) clusters (Cu<sub>n</sub>/PHI) by density functional theory calculations. The results show that Cu<sub>4</sub>/PHI with tetrahedral configuration has a better hydrogenation activity in the acetylene semi-hydrogenation reaction with H adsorbed in the vicinity of acetylene and subsequent intermediates in a non-bridge position, resulting in a smaller hydrogenation energy barrier. In addition, the top Cu atom transfers a large number of electrons to the bottom Cu atoms and PHI, and only a small number of electrons transfer to ethylene, resulting in weak adsorption of ethylene and easy desorption, which makes it good selectivity and therefore it can be used as a candidate catalyst for the semi-hydrogenation of acetylene. This study provides insights into the design of catalysts with suitable size clusters loaded on carbon nitride materials for efficient acetylene semi-hydrogenation reactions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114605"},"PeriodicalIF":3.9,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433652","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}
Keyi Wang, Yuanting Du, Yang Li, Xingkun Qi, Weijun Shan, Haibiao Yu, Ying Xiong
{"title":"F127 assisted synthesis of Bi promoted Co3O4 catalyst for catalyzing N2O decomposition in presence of impurity gases","authors":"Keyi Wang, Yuanting Du, Yang Li, Xingkun Qi, Weijun Shan, Haibiao Yu, Ying Xiong","doi":"10.1016/j.mcat.2024.114604","DOIUrl":"10.1016/j.mcat.2024.114604","url":null,"abstract":"<div><div>In this paper, Bi promoted Co<sub>3</sub>O<sub>4</sub> catalysts used for catalyzing N<sub>2</sub>O decomposition were successfully prepared by improved sol-gel method with the assistance of F127. It was found that the doping of additive Bi not only did not change the unique “Yardang Landform” microstructure of the 3.0F-Co<sub>3</sub>O<sub>4</sub>, but also prompted Co<sub>3</sub>O<sub>4</sub> to expose more active crystal planes, such as (422), (533) and (620). Moreover, the doping of the additive Bi also enhanced the catalyst's specific surface area, and further weakened the surface Co-O bond. The optimum 3.0F-Bi<sub>0.015</sub>Co catalyst achieved >88 % N<sub>2</sub>O conversion (2000 ppmv N<sub>2</sub>O/Ar, <em>GHSV</em>=20,000 <em>h</em><sup>−1</sup>) at 300 °C, and its corresponding <strong><em>TOF</em></strong> value increased from 1.50 × 10<sup>−3</sup> <em>s</em><sup>−1</sup> for 3.0F-Co<sub>3</sub>O<sub>4</sub> to 3.63 × 10<sup>−3</sup> <em>s</em><sup>−1</sup>. Meanwhile, the <strong><em>E<sub>a</sub></em></strong> of 3.0F-Bi<sub>0.015</sub>Co was as low as 47.0 kJ mol<sup>−1</sup>. Most importantly, the catalyst has good resistance to O<sub>2</sub> and H<sub>2</sub>O. Under the harsh condition (both 5 vol.% O<sub>2</sub>, 100 ppmv NO and 2 vol.% H<sub>2</sub>O were coexisted in the reaction system), the N<sub>2</sub>O conversion over the 3.0F-Bi<sub>0.015</sub>Co catalyst can be stable above 90 % at 400 °C.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114604"},"PeriodicalIF":3.9,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433653","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}
Kaihua Zhang , Changru Ma , Sebastien Paul , Jeremie Zaffran
{"title":"Unveiling the phenol direct carboxylation reaction mechanism at ZrO2 surface","authors":"Kaihua Zhang , Changru Ma , Sebastien Paul , Jeremie Zaffran","doi":"10.1016/j.mcat.2024.114606","DOIUrl":"10.1016/j.mcat.2024.114606","url":null,"abstract":"<div><div>In the present context of environmental concerns, sustainable solutions must be proposed to dispose of waste CO<sub>2</sub>, a well-known greenhouse gas. Among the various emerging projects, upgrading CO<sub>2</sub> molecule into high-value added chemicals appears to be very promising. More particularly, the carboxylation of aromatic compounds to (di-) acid aromatic monomers is of great interest for the high performance polymer industry. Focusing on the direct phenol carboxylation to <em>para</em>-hydroxybenzoic acid as a model reaction, the reactivity of ZrO<sub>2</sub> was investigated in this paper, this material being recently reported in various experimental works for its catalytic efficiency. For the first time, we established the phenol carboxylation mechanism at the surface of a metal oxide material, showing that the reaction can only proceed through an Eley-Rideal mechanism. In this mechanism, CO<sub>2</sub> is strongly chemisorbed at the surface, whereas phenol is physisorbed close to the CO<sub>2</sub> adsorbate. Besides, while the monoclinic and the tetragonal phases often coexist in ZrO<sub>2</sub> particles, we demonstrated that only the monoclinic geometry exhibits a substantial activity. However, the selectivity remains a major challenge, the <em>ortho</em>- isomer being the most abundant product, as in the original Kolbe-Schmitt method. While most of the processes generally reported in literature for the direct carboxylation of phenol are achieved in liquid media, a very few theoretical knowledge is available to describe such a process at solid surfaces. Therefore, we expect the present manuscript to be a pioneer work, aiming at providing a better understanding of metal oxide surface reactivity, paving the road to the rational design of efficient solid catalysts for aromatics carboxylation reactions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114606"},"PeriodicalIF":3.9,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433651","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}
Xiaoying Zhou , Shiyu Fang , Zihao Hu , Zuliang Wu , Jing Li , Wei Wang , Jiali Zhu , Shuiliang Yao , Erhao Gao
{"title":"Enhanced low-temperature methane oxidation over Pd supported Mn-doped NiO catalyst","authors":"Xiaoying Zhou , Shiyu Fang , Zihao Hu , Zuliang Wu , Jing Li , Wei Wang , Jiali Zhu , Shuiliang Yao , Erhao Gao","doi":"10.1016/j.mcat.2024.114611","DOIUrl":"10.1016/j.mcat.2024.114611","url":null,"abstract":"<div><div>This study introduces a novel catalyst system comprising Pd nanoparticles loaded onto Mn-doped NiO for the efficient oxidation of methane (CH<sub>4</sub>) at low temperatures. The loading of Pd nanoparticles onto the Mn-doped support has yielded a catalyst with exceptional activity and stability, as evidenced by the lowest T<sub>50</sub> temperature of 276 °C and a CH<sub>4</sub> conversion reaching 97% at 325 °C. The catalyst demonstrates optimized reaction kinetics with the lowest activation energy of 69.2 kJ mol<sup>–1</sup>. The catalyst's superior performance is attributed to the synergistic effects of the Pd/Mn-NiO composite, which include a higher Pd<sup>2+</sup>/Pd<sup>4+</sup> ratio, increased adsorptive oxygen concentration (O<sub>ads</sub>/O<sub>total</sub>), and a reduced Ni<sup>3+</sup>/Ni<sup>2+</sup> ratio. These characteristics collectively enhance the catalytic activity for CH<sub>4</sub> oxidation. The Mars-van Krevelen mechanism underpins the oxidation process, with Pd<sup>2+</sup> identified as the principal active site for CH<sub>4</sub> adsorption and dissociation. Diffuse reflectance infrared Fourier transform spectroscopy coupled with mass spectrometry elucidates the pathway of surface reactive oxygen species in the formation of key intermediates, such as formates, and underscores the accelerated decomposition of carbonate facilitated by the Pd modification on the Mn-NiO surface. The findings signify a significant advancement in the development of catalysts for environmental and energy-related applications, particularly in the mitigation of CH<sub>4</sub> emissions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114611"},"PeriodicalIF":3.9,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433767","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}
Wenyao Zhou, Rongjiao Tan, Changjun Yang, Bingguang Zhang, Kejian Deng
{"title":"Selective oxidation of benzyl alcohols photocatalyzed by asymmetric cobalt thioporphyrazine supported on alumina","authors":"Wenyao Zhou, Rongjiao Tan, Changjun Yang, Bingguang Zhang, Kejian Deng","doi":"10.1016/j.mcat.2024.114608","DOIUrl":"10.1016/j.mcat.2024.114608","url":null,"abstract":"<div><div>The sunlight-powered transformation of alcohols to corresponding carboxylic acids offers a feasible route for fine chemical synthesis. In this work, the asymmetric cobalt tri(2,3-bis(butylthio)maleonitrile)-(1,4-dithiin) porphyrazine (CoPz(SBu)<sub>6</sub>(dtn)) was synthesized, more importantly, its single crystal was further obtained by the solvent evaporation method. Then the asymmetric CoPz(SBu)<sub>6</sub>(dtn) supported on neutral Al<sub>2</sub>O<sub>3</sub> particles to form composite photocatalyst CoPz(SBu)<sub>6</sub>(dtn)@Al<sub>2</sub>O<sub>3</sub>, which possessed strong visible light absorption. Under simulated sunlight irradiation using a xenon lamp, the composite photocatalyst CoPz(SBu)<sub>6</sub>(dtn)@Al<sub>2</sub>O<sub>3</sub> exhibited excellent photocatalytic activity for selective oxidation of benzyl alcohol to benzoic acid in water under conditions of green H<sub>2</sub>O<sub>2</sub> as oxidant and K<sub>2</sub>CO<sub>3</sub> as additive. The conversion of benzyl alcohol was up to 53.8 % together with 99 % selectivity of benzoic acid over composite photocatalyst CoPz(SBu)<sub>6</sub>(dtn)@Al<sub>2</sub>O<sub>3</sub>. Meanwhile, this photocatalytic system had feasible substrate generalizability and excellent photocatalytic activity for substituted benzyl alcohols containing both electron-donating and electron-withdrawing substituents. The composite photocatalyst CoPz(SBu)<sub>6</sub>(dtn)@Al<sub>2</sub>O<sub>3</sub> exhibited excellent photocatalytic durability, which was confirmed by the recycling experiments. This work manifests the asymmetric thioporphyrazine as photocatalyst is feasible in implementing sunlight-powered selective transformation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114608"},"PeriodicalIF":3.9,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433769","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}
Fugui He , Xiangbin Kong , Tong Zhang , Yongning Yuan , Jianli Zhang , Xinhua Gao , Yurong He , Tiansheng Zhao
{"title":"Mechanistic insights of surface OH* modulation on methanol production with CO2 hydrogenation by iron-based catalyst","authors":"Fugui He , Xiangbin Kong , Tong Zhang , Yongning Yuan , Jianli Zhang , Xinhua Gao , Yurong He , Tiansheng Zhao","doi":"10.1016/j.mcat.2024.114599","DOIUrl":"10.1016/j.mcat.2024.114599","url":null,"abstract":"<div><div>The conversion of CO<sub>2</sub> into high-value-added chemicals via the Fischer-Tropsch Synthesis (FTS) reaction has gathered a lot of attention. The surface oxygenation environment is a significant factor affecting the catalyst performance. In this work, spin-polarized density-functional theory calculations have been used to investigate the adsorption and reactions of CO<sub>2</sub> and H to generate CH<sub>4</sub> and CH<sub>3</sub>OH on Fe<sub>5</sub>C<sub>2</sub>(510) surfaces with varying OH* coverage. On the pure Fe<sub>5</sub>C<sub>2</sub>(510) surface, CO<sub>2</sub> preferentially dissociates via direct dissociation, and the major C<sub>1</sub> species generated is CH<sub>4</sub>. At low OH* coverage, the preferential pathway for CO<sub>2</sub> dissociation changes from direct dissociation to the H-assisted route by the formation of COOH*. The major C<sub>1</sub> product of the reaction in this state is transferred to CH<sub>3</sub>OH. In addition, CO<sub>2</sub> hydrogenation reactions are facilitated by the OH* species. At high OH coverage, CO<sub>2</sub> preferentially dissociates through the HCOO* intermediates. However, it appears that the CO<sub>2</sub> hydrogenation reaction activity is suppressed. The results demonstrate that maintaining the surface environment with OH* and H* could be an indispensable measure to obtain the target product in the iron-based CO<sub>2</sub> Fischer-Tropsch Synthesis system.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114599"},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424037","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}
Yuan Zhang , Ali Kamali , Sheng Zhang , Tong Wang , Sooyeon Hwang , Aiysha Ashfaq , Lorelis Gonzalez-Lopez , Harrison Kraus , Jiayi Fu , Wenfei Zhang , Dionisios G. Vlachos , Mohamad I. Al-Sheikhly , Dongxia Liu
{"title":"Laser-engraved defects in TiO2 support: Enhancing reducibility and redox capability of Pt/TiO2 catalyst for reactive and selective hydrogenation","authors":"Yuan Zhang , Ali Kamali , Sheng Zhang , Tong Wang , Sooyeon Hwang , Aiysha Ashfaq , Lorelis Gonzalez-Lopez , Harrison Kraus , Jiayi Fu , Wenfei Zhang , Dionisios G. Vlachos , Mohamad I. Al-Sheikhly , Dongxia Liu","doi":"10.1016/j.mcat.2024.114602","DOIUrl":"10.1016/j.mcat.2024.114602","url":null,"abstract":"<div><div>Titanium dioxide (TiO<sub>2</sub>) has been studied as catalyst or catalyst support in catalysis. Its synthesis or modification approach controls the structural, optical, and electronic properties. Here we applied laser engraving to the anatase TiO<sub>2</sub> and studied the consequent changes in its structure and property as well as the properties of TiO<sub>2</sub> supported platinum (i.e., Pt/TiO<sub>2</sub>) catalyst. The laser engraving enlarged the particle size, formed rutile phase and created defects (i.e., oxygen vacancy (O<sub>v</sub>) and Ti<sup>3+</sup>) in anatase TiO<sub>2</sub>. This induced band gap change and enhanced visible light absorption. The defects created by laser engraving are stable and more reducible than those existed in the pristine TiO<sub>2</sub>. The defective TiO<sub>2</sub> is structurally stable and has great redox properties. The metal-support interaction in the Pt/defective TiO<sub>2</sub> catalyst is stronger than that of the pristine Pt/TiO<sub>2</sub> catalyst, which enabled higher reactivity and selectivity in hydrogenation of 3-nitrostyrene and furfuryl alcohol. Laser-engraved TiO<sub>2</sub> has been rarely studied for thermal catalysis. This work provides basic understanding of material properties and catalysis application of laser-engraved catalyst supports and catalysts in field of thermal catalysis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114602"},"PeriodicalIF":3.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424035","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}
Weijie Fu , Yiming He , Shuilian Liu , Jian Chen , Jie Ren , Ruiyan Sun , Zhenchen Tang , Chalachew Mebrahtu , Huanhao Chen , Feng Zeng
{"title":"Inverse supported Al2O3/Coº catalysts for enhanced CO2 hydrogenation","authors":"Weijie Fu , Yiming He , Shuilian Liu , Jian Chen , Jie Ren , Ruiyan Sun , Zhenchen Tang , Chalachew Mebrahtu , Huanhao Chen , Feng Zeng","doi":"10.1016/j.mcat.2024.114598","DOIUrl":"10.1016/j.mcat.2024.114598","url":null,"abstract":"<div><div>Inverse catalysts, characterized by their distinctive interfaces, demonstrate exceptional catalytic activity for CO<sub>2</sub> conversion. This study explores the synthesis of an Al-Co oxide/Co<sup>0</sup> inverse catalyst through the reduction of a Co-Al oxide with a high Co content, achieved by modulating the Co/Al ratio in the oxide precursor. The resulting inverse catalyst significantly enhances CO<sub>2</sub> hydrogenation, yielding increased production of methane, methanol, and ethanol, with a notable amplification in ethanol output. Amongst, the catalyst with a Co/Al ratio of 9:1 achieves high yields for methane (32,131 μmol/g, methanol (461 μmol/g), and ethanol (123 μmol/g). To elucidate the structure and reaction mechanism, the inverse catalyst was also characterized using a suite of techniques. It is posited that the abundance of active sites on the inverse catalyst, coupled with its moderate H binding affinity, facilitates CO<sub>2</sub> activation and conversion. This is particularly evident in the enhanced coupling of *HCOO and *CH<sub>3</sub> intermediates, which promotes ethanol synthesis. This research not only sheds light on the interactions between metal and metal oxide within Co-based catalysts for CO<sub>2</sub> hydrogenation but also proposes a facile method for crafting efficient catalysts for such processes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114598"},"PeriodicalIF":3.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424036","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}