Molecular Catalysis最新文献

{"title":"Organic N-hydroxyphthalimide catalyzes the selective aerobic oxidation of hydrocarbons promoted by the nonionic surfactants through hydrogen bonding effect","authors":"Ximai Zhang ,&nbsp;Fengkuan Ma ,&nbsp;Kui Jin ,&nbsp;Meifang Zhang ,&nbsp;Chen Chen ,&nbsp;Qiaohong Zhang ,&nbsp;Hongying Lü","doi":"10.1016/j.mcat.2025.115110","DOIUrl":"10.1016/j.mcat.2025.115110","url":null,"abstract":"<div><div>Metal-free catalytic selective oxidation of hydrocarbons is a green and challenging process for the manufacture of oxygen-containing chemicals. A nonionic surfactant of polyethylene glycol (PEG) was developed as the co-catalyst for <em>N</em>-hydroxyphthalimide (NHPI) to form a novel metal-free organic catalytic system NHPI/PEG, with which the efficient oxidation of a series of hydrocarbons including toluene, fluorene, ethylbenzene, and <em>p</em>-xylene was realized. PEG could facilitate the generation of active free radical phthalimide N-oxyl (PINO) through hydrogen bonding effect, and the decomposition of intermediate of phenylethyl hydroperoxide and oxidation of 1-phenylethanol could also be obviously improved especially at the presence of PEG. The present work provides a novel electronic promoter for the NHPI-based catalytic system and demonstrates the promoting efficiency of hydrogen bonding interactions on modulating the catalytic activity of organic catalytic system.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115110"},"PeriodicalIF":3.9,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143839437","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":"Exploring the hydrodeoxygenation of lignin β-O-4 dimer model compound and bio-oil by DFT and experimental studies","authors":"Yanjun Wen ,&nbsp;Foteini Zormpa ,&nbsp;Dmitry I. Sharapa ,&nbsp;Felix Studt ,&nbsp;Klaus Raffelt ,&nbsp;Nicolaus Dahmen","doi":"10.1016/j.mcat.2025.115134","DOIUrl":"10.1016/j.mcat.2025.115134","url":null,"abstract":"<div><div>Hydrodeoxygenation (HDO) is a pivotal process in the efficient utilization of biomass, with ruthenium (Ru) emerging as a highly effective catalyst for this reaction. A dimer model compound, more representative of bio-oil oligomers than monomers, was used to explore the HDO mechanism over a Ru catalyst through both density functional theory (DFT) calculations and experimental studies. Initially, the adsorption of 2-Phenylethyl phenyl ether (PPE) was examined through DFT, leading to the determination of an optimized structure. Subsequent calculations of the HDO reaction pathways on the Ru (0001) surface revealed that the β-O-4 linkage cleavage occurred with significantly low activation energy. For the experimental study, a Ru/Nb₂O₅ catalyst was synthesized using wet impregnation method. Characterization of this catalyst through scanning electron microscopy (SEM) and X-ray diffraction (XRD) confirmed its congruence with the DFT model. The catalytic performance of Ru/Nb₂O₅ was evaluated in the PPE HDO process, where it demonstrated high efficiency. The applicability of the Ru/Nb₂O₅ catalyst was extended to a real lignin bio-oil so as to further assess its effectiveness. This research provides a systematic study on PPE HDO over a Ru catalyst, illustrating the potential of using dimer model compounds in HDO mechanism investigations and the promising capabilities of Ru-based catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115134"},"PeriodicalIF":3.9,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834514","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":"Photocatalytic synthesis of dual acylmethylation derivates of indole[2,1-a]isoquinolinones via tandem cyclization/C3 acyl methylation","authors":"Zongbo Xie,&nbsp;Wenli Li,&nbsp;Weiwei Zhang,&nbsp;Ran Chen,&nbsp;Haibo Zhu,&nbsp;Zhanggao Le","doi":"10.1016/j.mcat.2025.115058","DOIUrl":"10.1016/j.mcat.2025.115058","url":null,"abstract":"<div><div>We developed a method for the synthesis of indole[2,1-a]isoquinolinones under visible light using sulfoxonium ylides for the first time. 2-Aryl-<em>N</em>-methacrylindole and sulfoxonium ylides were used as starting materials through free-radical addition tandem cyclization and C3 acylmethylation, which is a novel and practical method for the one-pot construction of structurally novel dual acylmethylation derivatives of indole[2,1-a]isoquinolinones. This method provides an efficient and pratical means to obtain valuable indole[2,1-a]isoquinolinones under mild reaction conditions. In addition, preliminary mechanistic explorations were performed, leading to the proposal of a plausible catalytic cycle mechanism.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115058"},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834510","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":"Rhombohedral Fe2O3/LaCoO3 nanomaterials as high-performance electrocatalysts for OER: Synthesis and electrochemical performance","authors":"Nouf Alharbi ,&nbsp;Vishal Burman ,&nbsp;Mahvish Khan ,&nbsp;Hajer Adam ,&nbsp;Manish Srivastava ,&nbsp;Shafiul Haque ,&nbsp;Sundeep S. Bhagwath ,&nbsp;Kurian Punnoose ,&nbsp;Mohammad Shariq","doi":"10.1016/j.mcat.2025.115124","DOIUrl":"10.1016/j.mcat.2025.115124","url":null,"abstract":"<div><div>The development of stable, non-noble, and sustainable nanomaterials offers a viable pathway for enhancing water electrolysis operations, especially in facilitating efficient Oxygen Evolution Reaction (OER). In this study, we have prepared a rhombohedral composite nanomaterial (Fe₂O₃/LaCoO₃) for the OER by co-precipitation method. Samples were thoroughly analyzed using multiple techniques to ensure comprehensive characterization, including X-Ray Diffraction (XRD) for crystallographic structure determination, Scanning Electron Microscopy (SEM) for surface morphology observation, Energy Dispersive X-ray Spectroscopy (EDX) for elemental composition analysis, mapping analysis to visualize spatial distribution of elements, and Fourier Transform Infrared Spectroscopy (FTIR) for identifying functional groups and chemical bonds. Prepared electrocatalyst reveals robust OER performance with an overpotential of 311 mV to achieve the 10 mAcm⁻² current density in alkaline media. Significantly, this catalyst offers a low Tafel slope of 76 mV dec^‑1 and a charge transfer resistance of 532 Ω with excellent Linear Sweep Voltammetry (LSV) cycling stability. The improved electrocatalytic performance results from the synergistic interaction among La, CoO₃, and Fe₂O₃, which typically enhances the overpotential, charge-mass transport, and stability. This strategy offers a viable pathway for synthesizing and optimizing nanomaterials for advanced electrochemistry.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115124"},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834511","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":"Unraveling the role of metal promoters (Zn, Cu, Co, Mn and Mg) in CO2 hydrogenation to light olefins over Fe-K catalysts","authors":"Haonan Zu,&nbsp;Huashuai Wu,&nbsp;Jiarong Tian,&nbsp;Ao Li,&nbsp;Junwen Wang","doi":"10.1016/j.mcat.2025.115104","DOIUrl":"10.1016/j.mcat.2025.115104","url":null,"abstract":"<div><div>Efficient CO₂ utilization is crucial for mitigating environmental concerns. In this study, the promoting effect of transition metal (Zn, Cu, Co and Mn) and alkaline earth metal Mg on Fe-K catalysts for CO₂ hydrogenation to light olefins were investigated. A series of Fe-K catalysts with different metal modified were prepared using the activated carbon template method proposed in this work. This method greatly improves catalyst dispersion, enabling the synthesis of high-performance Fe-K catalysts. The promoter-dependent mechanisms governing catalyst performance and selectivity were revealed. Zn promotion significantly enhances Fe dispersion and electron transfer, resulting in electron-rich Fe₅C₂ and exceptional light olefin selectivity with a value of 35.00 %. Co maximizes CO₂ conversion (46.88 %). However, Co promotes H₂ dissociation, enhancing the formation of n-alkane products and reducing C₂-C₄ olefin-to-paraffin ratio. Adding Cu, while greatly enhancing the reduction and carburization behavior of iron oxides, significantly weakens the adsorption of CO₂. The strong interaction between Mn and iron species leads to a complex reduction and carburization process of Fe-K catalyst and greatly reduces its basicity. The addition of Cu, Mg, and Mn greatly promote C-C coupling towards heavier hydrocarbons. These findings provide a comprehensive understanding of promoter roles and offer a rational strategy for designing advanced Fe-K catalysts for tailed CO₂ hydrogenation product distributions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115104"},"PeriodicalIF":3.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834509","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":"Enhanced oxygen reduction reaction activity and stability of the PtCo/C catalysts with Pt-enriched surface layer: an investigation of the effect on acid-leaching during the de-alloying process","authors":"Zhen Meng ,&nbsp;Juntao Pan ,&nbsp;Yuwen Xu ,&nbsp;Jiani He ,&nbsp;Hang Zhan ,&nbsp;Shasha Luo ,&nbsp;Lijun Yang ,&nbsp;Jianhuang Zeng","doi":"10.1016/j.mcat.2025.115122","DOIUrl":"10.1016/j.mcat.2025.115122","url":null,"abstract":"<div><div>One of the key issues hinders large-scale commercial application of the proton exchange membrane fuel cells is the unsatisfactory performance of the Pt cathodic electrocatalysts for oxygen reduction reaction (ORR). The generally accepted solution is to alloy Pt with transitional metals at high temperatures. These catalysts are commonly prepared through high temperature annealing followed by de-alloying in acidic electrolytes. This work focuses on the effects of acid de-alloying on the structure of the Pt₂Co/C catalysts and correlates with their activity and stability for ORR. It is found that the overall performance of the Pt₂Co/C is greatly affected by the acid treatment temperatures (40, 60 and 80 °C). When the Pt₂Co/C is treated at 40 °C in HNO₃, the Pt₂Co/C-40 displays the highest activity and stability, which is double-confirmed both by half-cell (rotating disk electrode) and single cell (membrane electrode assembly) evaluations. The catalyst treated under this condition reveals an alloyed structure with 3–4 Pt atomic layers and an optimal particle size of 4.8 nm. Meanwhile, the performance enhancement is possibly also aided by the introduced N-sources during synthesis. This synthesis offers an easier and scalable manner to produce Pt-alloyed catalyst with enhanced activity and stability.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115122"},"PeriodicalIF":3.9,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829083","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":"Reaction-induced reconstruction and redispersion of Ni@C catalyst for enhancing HMF electrooxidation","authors":"Xinyu Liu ,&nbsp;Yuhang Li ,&nbsp;Mengli Zhou ,&nbsp;Youqin Jiang ,&nbsp;Haojie Tian ,&nbsp;Zhimin Wu ,&nbsp;Qiying Liu ,&nbsp;Jianchun Jiang","doi":"10.1016/j.mcat.2025.115131","DOIUrl":"10.1016/j.mcat.2025.115131","url":null,"abstract":"<div><div>The electrocatalytic conversion of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) offers a highly effective and eco-friendly pathway for the utilization of biomass resources. For the widely studied Ni-based electrodes, enhancing their catalytic activity remains challenging due to the sluggish phase transition of Ni(OH)₂ to the active NiOOH. Here, we present a model catalyst of Ni nanoparticles encapsulated by a carbon layer (Ni@C), systematically investigate the role of active sites formed by reconstruction and redispersion in enhancing the electrocatalytic activity, and further explore the effect of HMF concentration on Ni@C reconstruction and redispersion. The encapsulated carbon layer contributes to nickel grain reconstruction and redispersion to form Ni³⁺ sites, thereby increasing the electrochemically active surface area. A combination of in-situ Raman, HRTEM and XPS characterization analyses showed that high concentrations of HMF electrolytes promoted faster reconstruction and redispersion of Ni grains encapsulated within the carbon layers to generate smaller-sized NiOOH grains, thus significantly improving HMF oxidation. This study establishes a novel catalytic pathway for enhancing HMF electrooxidation performance by reaction-induced reconstruction and redispersion of Ni@C catalyst.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115131"},"PeriodicalIF":3.9,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829082","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":"Photochemical synthesis of highly efficient Pt/TiO2 catalyst for thermal CO2 reduction to CO","authors":"Zhanglong Guo ,&nbsp;Li Wang ,&nbsp;Jiacheng Zhang ,&nbsp;Hongmei Zhou ,&nbsp;Jianli Yang ,&nbsp;Xin Xiao","doi":"10.1016/j.mcat.2025.115109","DOIUrl":"10.1016/j.mcat.2025.115109","url":null,"abstract":"<div><div>Supported platinum (Pt) catalysts are crucial for thermal CO₂ reduction, yet traditional preparation methods often yield low catalytic activity. This study addresses this challenge by developing a photochemical deposition method to synthesize highly efficient Pt/TiO₂ catalysts (Pt/TiO₂-L) using only water as the solvent. The Pt/TiO₂-L catalyst exhibited significantly higher CO₂ conversion rates as 65 % at 600 °C and operational stability compared to traditionally prepared catalysts. TEM result revealed uniform dispersion of small Pt nanoparticles (around 1 nm) on the TiO₂ support. XPS analysis showed a higher Pt surface content in Pt/TiO₂-L, resulting in more active sites for CO₂ reduction. In-situ CO-DRIFTS confirmed enhanced CO adsorption on Pt/TiO₂-L due to its higher surface Pt content. This work demonstrates that the photochemical route is an effective and simple method for synthesizing efficient Pt/TiO₂ catalysts for thermal CO₂ reduction, offering promising prospects for industrial application in green chemistry.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115109"},"PeriodicalIF":3.9,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820502","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":"Insights into the role of transition metal M (M = Mo, Fe, Ru, Cu, Pt) in acetone hydrogenation on M@Ni(111) single-atom surface alloys: A DFT study","authors":"Guixi Liu ,&nbsp;Qinwei Zhang ,&nbsp;Zixuan Zhao ,&nbsp;Qinmei Fan ,&nbsp;Lei Chen ,&nbsp;Yongkang Ge ,&nbsp;Xiaolei Wang","doi":"10.1016/j.mcat.2025.115111","DOIUrl":"10.1016/j.mcat.2025.115111","url":null,"abstract":"<div><div>The unsaturated carbonyl hydrogenation is crucial in the chemical industry. This study investigates acetone hydrogenation on M@Ni(111) single-atom surface alloys (<em>M</em>=Mo, Fe, Ru, Cu, Pt) by density functional theory (DFT). The adsorption energies of acetone and intermediates indicate that Mo@Ni(111) has the highest adsorption stability. Additionally, the d-band center on Mo@Ni(111) is the highest, contributing to enhanced hydrogenation activity. Activation energies and elementary reaction rates are calculated and compared for both the Alkoxy and Hydroxy routes. The Alkoxy route shows lower energy barriers on Mo@Ni(111), Fe@Ni(111), and Ru@Ni(111), while the Hydroxy route has lower energy barriers on other two surfaces. Microkinetic analysis reveals that the Alkoxy route consistently shows higher reaction rates across all surfaces, with rate order: Mo@Ni(111) &gt; Fe@Ni(111) &gt; Ru@Ni(111) &gt; Cu@Ni(111) &gt; Pt@Ni(111). Notably, Mo@Ni(111) is identified as the most efficient catalyst. Further analysis of charge density differences and projected density of states (PDOS) shows that Mo doping causes significant surface charge transfer, thereby enhancing the reactivity of Mo@Ni(111) relative to other catalysts. The distinct electronic structures of the metal surfaces provide insights into their catalytic behavior, highlighting the role of surface modifications in optimizing catalytic performance.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115111"},"PeriodicalIF":3.9,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820418","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":"Construction of electron-rich Co centers and abundant redox pairs in MnO2/CoMn2O4 heterointerfaces for PMS activation and water purification","authors":"Shuo Wang ,&nbsp;Xingrong Li ,&nbsp;Hongyao Zhao ,&nbsp;Zichen Ma ,&nbsp;Danhong Shang ,&nbsp;Linzhi Zhai ,&nbsp;Xiang Liu ,&nbsp;Feng Zeng ,&nbsp;Jianming Pan ,&nbsp;Yanyun Wang ,&nbsp;Fu Yang","doi":"10.1016/j.mcat.2025.115100","DOIUrl":"10.1016/j.mcat.2025.115100","url":null,"abstract":"<div><div>Multiphase catalysts with heterointerfaces have shown compelling potential in catalyzing oxidative mineralization of pollutants. In particular, the interfacial electron communication of heterointerfaces is beneficial for activation of reactant molecules through promotive interfacial electron transfer efficiency. In this study, a MnO₂/CoMn₂O₄ heterojunction catalyst was constructed for the electron-rich Co centers and abundant redox pairs. Benefiting from the synergistic interaction between cobalt (Co²⁺/Co³⁺) and manganese (Mn²⁺/Mn³⁺/Mn⁴⁺) at the active sites, as well as the electron density difference between the interfaces of the two phases, a significant enhancement of the catalytic activity for peroxymonosulfate (PMS) activation was achieved. Systematic characterization analysis revealed that the catalyst has highly active catalytic sites characterized by electron-rich Co²⁺, and the electron-donating property of the high-electron-density Co²⁺ active sites in the A site of spinel CoMn₂O₄ promotes the efficient transfer of electrons and the rapid generation of reactive oxygen species (ROS) from PMS activation. More exposed catalytic active sites and significantly lower interfacial mass transfer resistance further enhanced the activation performance of the catalysts for bisphenol A degradation by these ROS. The optimal MnO₂/CoMn₂O₄–5 exhibited a optimal BPA degradation activity (86 %, k_obs = 0.316 min^-1) and excellent resistance to anionic interference. The results of free radical quenching experiments indicated that single linear oxygen (¹O₂) and hydroxyl radical (·OH) were the main active substances for PMS activation and BPA degradation. This study provides meaningful insights into the improvement of heterojunction interfacial systems for catalytic efficiency enhancement and environmental remediation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115100"},"PeriodicalIF":3.9,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143816759","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}