Molecular Catalysis最新文献

A combined DFT-Experimental study on FSP-made Ru/Ti-SiO2 catalysts for CO2 methanation fsp制备Ru/Ti-SiO2 CO2甲烷化催化剂的联合dft -实验研究

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-05 DOI: 10.1016/j.mcat.2025.115179

Okorn Mekasuwandumrong , Tinnakorn Saelee , Jakapob Noppakhun , Meena Rittiruam , Patcharaporn Khajondetchairit , Damien P. Debecker , Supareak Praserthdam , Piyasan Praserthdam

{"title":"A combined DFT-Experimental study on FSP-made Ru/Ti-SiO2 catalysts for CO2 methanation","authors":"Okorn Mekasuwandumrong , Tinnakorn Saelee , Jakapob Noppakhun , Meena Rittiruam , Patcharaporn Khajondetchairit , Damien P. Debecker , Supareak Praserthdam , Piyasan Praserthdam","doi":"10.1016/j.mcat.2025.115179","DOIUrl":"10.1016/j.mcat.2025.115179","url":null,"abstract":"<div><div>Flame spray pyrolysis (FSP) was employed to synthesize Ti-modified SiO₂ in a single step, serving as the support for Ru-based catalysts in CO₂ methanation reactions. The addition of Ti led to the formation of anatase and rutile TiO₂ phases, enhancing the catalytic activity of Ru/Ti-SiO₂ catalysts. Benchmarking between Ru/Ti-SiO₂ catalysts of various Ti concentrations prepared using one-step FSP techniques indicated significantly higher catalytic activity for the impregnation-made catalysts compared to the FSP-made ones, where diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed different CH₄ formation mechanisms between two techniques. For FSP-made catalysts, it predominantly occurred through the CO route, whereas the impregnation-made proceed via both the dissociative adsorption of CO₂ (CO route) and through surface formate species formation. To explain the effect of Ti loading on Ru/SiO₂ catalysts, a multiscale analysis combining density functional theory (DFT) and microkinetic modeling was performed to study the adsorption behavior of CO₂ on different catalysts. The results revealed that a high amount of Ti reduced the adsorption strength of CO₂ on Ru/SiO₂ catalysts, indicating a modified interaction between CO₂ and the catalyst surface.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"582 ","pages":"Article 115179"},"PeriodicalIF":3.9,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904092","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}

引用次数: 0

A review of methods and strategies for NO and CO pollutant removal from flue gas using copper-based catalysts: Mechanisms and performance 利用铜基催化剂去除烟气中NO和CO污染物的方法和策略综述：机理和性能

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-05 DOI: 10.1016/j.mcat.2025.115174

Ruoxin Li , Jiuhong Wei , Jun Liu , Bin Jia , Jiaxuan Liu , Ying Wang , Yuqiong Zhao , Guoqiang Li , Guojie Zhang

{"title":"A review of methods and strategies for NO and CO pollutant removal from flue gas using copper-based catalysts: Mechanisms and performance","authors":"Ruoxin Li , Jiuhong Wei , Jun Liu , Bin Jia , Jiaxuan Liu , Ying Wang , Yuqiong Zhao , Guoqiang Li , Guojie Zhang","doi":"10.1016/j.mcat.2025.115174","DOIUrl":"10.1016/j.mcat.2025.115174","url":null,"abstract":"<div><div>With the rapid acceleration of industrialization, the emission of nitrogen oxides (NO<sub>x</sub>) and carbon monoxide (CO) has emerged as a pressing global environmental issue, posing significant threats to ecosystems and human health. Copper-based catalysts have garnered substantial attention in the field of multi-pollutant synergistic treatment due to their abundant availability, low cost, and superior catalytic performance. This paper provides a comprehensive review of the recent advancements in copper-based catalysts for the removal of NO<sub>x</sub> and CO from flue gas, with a focus on their applications in selective catalytic reduction (SCR), CO catalytic oxidation, and bifunctional co-catalysis. Through an in-depth analysis of key factors influencing catalytic performance—such as valence modulation, morphological structure design, optimization of preparation methods, auxiliary doping, and adjustment of metal ratios—the critical roles of various catalyst properties are elucidated. These include redox capabilities, acidic nature, surface oxygen vacancy concentration, and active site dispersion in the catalytic process. Furthermore, this paper explores in detail the reaction mechanisms and sulfur-resistant properties of copper-based catalysts employed in several strategies for NO<sub>x</sub> and CO removal, highlighting the potential of bifunctional catalysts for simultaneous NO<sub>x</sub> and CO abatement. Significant progress has been achieved in enhancing low-temperature activity and stability through the optimization of preparation processes, intermetallic interactions, and structural design of copper-based catalysts. These advancements provide crucial theoretical insights and practical guidance for the development of future environmental treatment technologies, paving the way for more efficient and sustainable solutions to address global pollution challenges.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"582 ","pages":"Article 115174"},"PeriodicalIF":3.9,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904093","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}

引用次数: 0

Advances in the preparation and application of nanoconfined metal catalysts composed of porous materials 多孔材料纳米金属催化剂的制备与应用研究进展

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-03 DOI: 10.1016/j.mcat.2025.115175

Liang Li , Jiamin Liang , Jinwei Zhu , Yongxiang Zhao , Hao Wang

{"title":"Advances in the preparation and application of nanoconfined metal catalysts composed of porous materials","authors":"Liang Li , Jiamin Liang , Jinwei Zhu , Yongxiang Zhao , Hao Wang","doi":"10.1016/j.mcat.2025.115175","DOIUrl":"10.1016/j.mcat.2025.115175","url":null,"abstract":"<div><div>Nanoconfinement catalysis is becoming a research hotspot in the field of catalytic reactions due to its potential to enhance catalytic performance. Porous nanoconfined catalysts are designed by dispersing nanoparticles of active metal into porous support through various synthesis methods. This kind of catalyst can utilize the confinement effect of the pores to precisely regulate the dispersion and particle size of the metal particles, and then improve their catalytic activity and stability. During the process of catalytic reaction, the confinement effect of the pores in porous materials can effectively optimize the electronic states of the metal active components. Furthermore, the shape-selectivity of the pore channels can significantly improve the selectivity of the reaction products. This paper provides a comprehensive review of recent synthesized strategies for pore-confined metal nano-catalysts and their catalytic applications, and then delves into the mechanism by which the pore-confinement effect enhances catalytic activity, product selectivity, and the stability of catalysts. Specifically, the discussion is focused on various synthesis methods for pore-confined catalysts, including in situ encapsulated, core-shell structured, two-dimensional layered, and single-atom anchored catalysts, as well as recent advances of these catalysts in different catalytic reactions. Finally, the future prospect is proposed in order to provide a guidance for the development and application of pore-confined catalysts in catalytic reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"582 ","pages":"Article 115175"},"PeriodicalIF":3.9,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898736","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}

引用次数: 0

A DFT study on the active surfaces of the ZnGa2O4 spinel catalyst for CO2 hydrogenation to methanol ZnGa2O4尖晶石催化剂活性表面的DFT研究

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-03 DOI: 10.1016/j.mcat.2025.115166

Ziqi Tang , Yuanjie Bao , Zhangqian Wei , Shenggang Li

{"title":"A DFT study on the active surfaces of the ZnGa2O4 spinel catalyst for CO2 hydrogenation to methanol","authors":"Ziqi Tang , Yuanjie Bao , Zhangqian Wei , Shenggang Li","doi":"10.1016/j.mcat.2025.115166","DOIUrl":"10.1016/j.mcat.2025.115166","url":null,"abstract":"<div><div>In this work, we constructed the low Miller index surfaces of (100), (001), (111), and (110) of the ZnGa<sub>2</sub>O<sub>4</sub> spinel catalyst. Through extensive DFT calculations, we found that the oxygen vacancy (V<sub>O</sub>) formation energies on the (100) and (001) surfaces were <1.0 eV, whereas those on the (111) and (110) surfaces were >3.0 eV. We further examined the dissociation of molecular hydrogen (H<sub>2</sub>) on these surfaces, and found that H<sub>2</sub> homolytic dissociation tended to occur on surfaces with lower V<sub>O</sub> formation energies, while H<sub>2</sub> heterolytic dissociation were favored on those with higher V<sub>O</sub> formation energies. CO<sub>2</sub> adsorption and activation on the different surfaces of the ZnGa<sub>2</sub>O<sub>4</sub> spinel catalyst were investigated, and on surfaces with lower V<sub>O</sub> formation energies, CO<sub>2</sub> adsorbs in a linear configuration (ln-CO<sub>2</sub>*), while on surfaces with higher V<sub>O</sub> formation energies, CO<sub>2</sub> adopts in a bent adsorption geometry (bt-CO<sub>2</sub>*) and is easier to dissociate. For HCOO formation from ln-CO<sub>2</sub>* + H*, the (110) surface has the lowest energy barrier, so it is likely the most active surface for CO<sub>2</sub> hydrogenation to methanol (CH<sub>3</sub>OH). Thus, we compared the CH<sub>3</sub>OH formation pathway on the ZnGa<sub>2</sub>O<sub>4</sub>(110) surface with the pathways for direct and indirect CO<sub>2</sub> dissociation, and predicted it to favor CH<sub>3</sub>OH production. Our calculations reveal the active surfaces of the ZnGa<sub>2</sub>O<sub>4</sub> spinel catalyst for CO<sub>2</sub> hydrogenation to CH<sub>3</sub>OH, and provide insights into the experimentally observed high CH<sub>3</sub>OH selectivity, which should be important for the rational design of Zn-based spinel catalysts for this reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"582 ","pages":"Article 115166"},"PeriodicalIF":3.9,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898719","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}

引用次数: 0

Spray drying synthesis of stable Cu catalyst supported on carbon with high C2 product selectivity in CO2 electrolysis 喷雾干燥法制备碳负载Cu催化剂的研究

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-03 DOI: 10.1016/j.mcat.2025.115162

Lili Yang, Jinghao Lu, Chao Wang, Lianying Zhang, Chuanhui Zhang, Xingyun Li, Hongliang Li, Xiu Song Zhao

{"title":"Spray drying synthesis of stable Cu catalyst supported on carbon with high C2 product selectivity in CO2 electrolysis","authors":"Lili Yang, Jinghao Lu, Chao Wang, Lianying Zhang, Chuanhui Zhang, Xingyun Li, Hongliang Li, Xiu Song Zhao","doi":"10.1016/j.mcat.2025.115162","DOIUrl":"10.1016/j.mcat.2025.115162","url":null,"abstract":"<div><div>Electrocatalytic carbon dioxide (CO<sub>2</sub>) reduction is an appealing option that offers advantages of converting greenhouse gas CO<sub>2</sub> into value-added hydrocarbon products while storing green energy. Copper (Cu) is a unique catalyst that has adequate ability for adsorption and activation of CO<sub>2</sub>, as well as important intermediate species for forming multi-carbon (C<sub>2+</sub>) products. In particular, monovalent Cu(I) is deemed to be responsible for C-C coupling to form C<sub>2+</sub> products. However, oxidation state copper species are unstable under the CO<sub>2</sub> electrolysis conditions, tending to be reduced along with surface reconstruction. It is therefore important to develop a robust catalyst synthesis method to enhance the stability of Cu-based catalysts. Here, we demonstrate a spray-drying method for the synthesis of carbon-supported Cu catalysts for the electrocatalytic CO<sub>2</sub> reduction reaction. This method is scalable and cost-effective, allowing one to realize mass production of carbon-supported Cu catalysts. A catalyst sample thus synthesized exhibits a Faraday efficiency of C<sub>2</sub> products (e.g., ethylene, ethanol and acetic acid) as high as 85.8 %. <em>In-situ</em> attenuated total reflection-surface-enhanced infrared absorption spectroscopy and surface-enhanced Raman spectroscopy characterization results reveal that the porous carbon support stabilizes Cu<sub>2</sub>O/CuO nanoparticles, facilitate CO<sub>2</sub> adsorption, enrich local important intermediates for the C-C coupling reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"582 ","pages":"Article 115162"},"PeriodicalIF":3.9,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898745","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}

引用次数: 0

Surface oxygen vacancy-dependent and solvent effect on selective oxidation of benzyl alcohol to benzaldehyde over spinel CuMn2O4 with molecular oxygen 表面氧空位依赖性和溶剂对尖晶石CuMn2O4选择性氧化苯甲醇制苯甲醛的影响

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-03 DOI: 10.1016/j.mcat.2025.115172

Weitao Wang , Kang Wang , Huan Wang , Jiaqi Zhu , Zhen-Hong He , Zhao-Tie Liu

引用次数: 0

Visible-light-mediated oxidant-free tandem acylmethylation/ipso-spirocyclization of N-arylpropiolamides: Access to 3-acylmethyl azaspiro[4,5]trienones 可见光介导的n -芳基丙酰胺的无氧化剂串联酰基甲基化/ipso-螺旋环化：获得3-酰基甲基azspiro[4,5]三烯酮

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-02 DOI: 10.1016/j.mcat.2025.115120

Binfeng Zhu , Guokai Li , Mingzhu Li , Deyu Bao , Jingchao Chen , Devendar Ponnam , Baomin Fan

引用次数: 0

Tuning Co2+ active sites over Co3O4 for boosting electrocatalytic oxygen evolution in neutral media 调节Co3O4上的Co2+活性位点促进中性介质中电催化析氧

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-02 DOI: 10.1016/j.mcat.2025.115165

Juan Zhang , Lian Duan , Junshan Lin , Ruiling Du , Gen Chen , Qing Kang , Ning Zhang

{"title":"Tuning Co2+ active sites over Co3O4 for boosting electrocatalytic oxygen evolution in neutral media","authors":"Juan Zhang , Lian Duan , Junshan Lin , Ruiling Du , Gen Chen , Qing Kang , Ning Zhang","doi":"10.1016/j.mcat.2025.115165","DOIUrl":"10.1016/j.mcat.2025.115165","url":null,"abstract":"<div><div>Electrochemical water splitting is a promising hydrogen production technology, with the oxygen evolution reaction (OER) as the key step. This study focuses on enhancing the OER activity under neutral conditions using acid-treated Co<sub>3</sub>O<sub>4</sub> (A-Co<sub>3</sub>O<sub>4</sub>) as a viable alternative to noble metal electrocatalysts. We synthesized acid-treated Co<sub>3</sub>O<sub>4</sub> with a tunable Co<sup>2+</sup>/Co<sup>3+</sup> atomic ratio from 0.63 to 1.69. The A-Co<sub>3</sub>O<sub>4</sub> exhibited an overpotential of only 438 mV at a current density of 10 mA cm<sup>–</sup><sup>2</sup> with sustained activity for over 70 h. <em>In-situ</em> Raman spectroscopy analysis indicated that Co<sup>2+</sup> sites were conducive to forming highly oxidative γ-CoOOH and stabilizing the CoOOH phase under OER conditions. Density functional theory (DFT) calculations showed that Co<sup>2+</sup> sites on the surface of Co<sub>3</sub>O<sub>4</sub> significantly lower the Gibbs free energy barrier of the rate-determining step compared to Co<sup>3+</sup> sites. This study proposes a simple and effective acid-treatment method to enhance the OER activity of Co<sub>3</sub>O<sub>4</sub>, paving the way for its application in neutral seawater electrolysis and contributing to the development of cost-effective hydrogen production technologies.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"582 ","pages":"Article 115165"},"PeriodicalIF":3.9,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898744","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}

引用次数: 0

Cu NPs@covalent organic framework: An efficient photocatalyst for light-assisted selective formylation of phenol derivatives utilizing carbon dioxide Cu NPs@covalent有机骨架：利用二氧化碳进行光辅助选择性甲酰化苯酚衍生物的高效光催化剂

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-02 DOI: 10.1016/j.mcat.2025.115154

Surya Das , Priyanka Sarkar , Titu Mondal , Nasir A Siddiqui , Sk. Manirul Islam

{"title":"Cu NPs@covalent organic framework: An efficient photocatalyst for light-assisted selective formylation of phenol derivatives utilizing carbon dioxide","authors":"Surya Das , Priyanka Sarkar , Titu Mondal , Nasir A Siddiqui , Sk. Manirul Islam","doi":"10.1016/j.mcat.2025.115154","DOIUrl":"10.1016/j.mcat.2025.115154","url":null,"abstract":"<div><div>Our study presents a novel synthetic approach for the visible-light-assisted photocatalytic production of 2-hydroxybenzaldehyde from phenol via CO<sub>2</sub> reduction, using copper nanoparticles (Cu NPs)-incorporated two-dimensional covalent organic framework (TR-PDA COF) photocatalyst. The Cu@TR-PDA catalyst exhibited a low band gap energy (2.14 eV), enabling efficient visible light absorption and photocatalytic activity. Under optimized conditions, this catalyst achieved 87 % conversion of phenol to 2-hydroxybenzaldehyde under 20 W white LED light. The reaction was light-dependent and required a base. Mechanistic studies revealed that formaldehyde (HCHO), generated from CO<sub>2</sub> photoreduction, served as a key intermediate, which reacted with phenol to form the desired product. Furthermore, the Cu@TR-PDA catalyst demonstrated excellent reusability over six cycles, and showed minimal metal leaching, confirming its heterogeneous nature. This work offers a promising strategy for the sustainable conversion of CO<sub>2</sub> into valuable chemicals using a metal-based photocatalyst under visible light.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"582 ","pages":"Article 115154"},"PeriodicalIF":3.9,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143895034","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}

引用次数: 0

Photocatalytic synthesis of carbamoylated chroman-4-ones via radical cascade cyclization of 2-(allyloxy)arylaldehydes and oxamic acids 2-烯丙氧基芳醛和肟酸自由基级联环化光催化合成氨基甲酰化铬-4-酮

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-05-02 DOI: 10.1016/j.mcat.2025.115168

Aixin Wang, Fengtian Wu, Guofang Jiang, Zhanggao Le, Zongbo Xie

引用次数: 0