Article
Chemistry, Inorganic & Nuclear
Panyapat Ponchai, Kanyaporn Adpakpang, Sareeya Bureekaew
Summary: The utilization of metal-organic frameworks as heterogeneous catalysts is crucial due to their abundant catalytic sites and well-defined porous structures. In the case of the highly robust [Cu-3(trz)(3)(mu(3)-OH)(OH)(2)(H2O)(4)] center dot 2H(2)O catalyst, selective oxidation of cyclohexene to allylic products with high yield and selectivity is achieved, likely through homolytic activation of H2O2. This finding highlights the unique features of MOFs for efficient catalysis of cyclohexene oxidation.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Julia Bueker, Xiubing Huang, Johannes Bitzer, Wolfgang Kleist, Martin Muhler, Baoxiang Peng
Summary: The Cu single atoms loaded on a graphitic carbon nitride matrix showed excellent catalytic performance in liquid-phase cyclohexene oxidation, with high conversion and reusability. Addition of hydroquinone as a radical scavenger confirmed the radical mechanism of the oxidation process.
Article
Chemistry, Physical
Julia Bueker, Martin Muhler, Baoxiang Peng
Summary: This concept article provides a comprehensive overview of recent advances in selective oxidation of cyclohexene using heterogeneous transition metal-based catalysts and environmentally benign oxidants.
Article
Chemistry, Physical
Nelly F. Nunheim, Werner R. Thiel
Summary: Systematic optimization of the Ru-catalyzed oxidation of alcohols using TBHP as the oxidizing agent was carried out. A sustainable protocol was developed using a water/tert-butanol mixture as the solvent and a syringe pump for continuous addition of the oxidizing agent, resulting in high yields and selectivity.
Article
Engineering, Chemical
Jitendra Diwakar, Selvamani Arumugam, Bhavna Saini, Anup Prakash Tathod, Nagabhatla Viswanadham
Summary: Mesoporous titanium-containing alumino-silicate materials with various Ti/Si ratios (AlSi-Ti(n); n = Ti/Si mole ratio) were synthesized using a novel single-step sodium-free method. The characterized materials showed ordered mesoporous structure and uniformly dispersed Ti species in +4 and +3 oxidation states, making them suitable for selective oxidation of allylic C-H bond. The prepared mesoporous Ti-AlSi(n) samples exhibited excellent activity in the oxidation of cyclohexene, achieving 100% conversion and 100% selectivity to ketone-alcohol (KA) oil under mild reaction conditions (35 degrees C and 30 min reaction time). The AlSi-Ti(0.05) material has potential as a promising catalyst for selective oxidation of cyclohexene.
CHINESE JOURNAL OF CHEMICAL ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Mingxing Duan, Xinguo Wang, Wenjing Peng, Dongjie Liu, Qingyan Cheng, Qiusheng Yang
Summary: In this study, a heterogeneous, recoverable catalyst of Co(II)-L@nano-SiO2 was synthesized and investigated for the oxidation of cyclohexene under mild conditions. The results showed excellent catalytic activity with high selectivity for the major products, and the mechanism involved allylic oxidation and overoxidation reactions were confirmed by DFT calculations.
Article
Chemistry, Applied
Pilar Yeste, M. Amine Fellak, Hilario Vidal, Francisco M. Guerra, F. Javier Moreno-Dorado, Jose M. Gatica
Summary: In this study, a copper-iron mixed oxide was deposited on cordierite honeycomb monoliths using the washcoating procedure, creating an excellent heterogeneous catalyst. The prepared catalyst exhibited high yield and stability in the selective production of allylic ester in the Kharasch-Sosnovsky oxidation of cyclohexene with benzoic acid. The use of a structured catalyst offers an interesting alternative to homogeneous catalysis in synthetic chemistry.
Article
Chemistry, Physical
Julia Bueker, Baoxiang Peng
Summary: Uncatalyzed liquid-phase oxidation of cyclohexene was studied to investigate its autoxidation kinetics and reaction mechanisms. The dominating reaction step was found to transition at different temperatures. Cyclohexenyl radicals played a decisive role in the absence of any catalyst. High pressures inhibited cyclohexene conversion, while the decomposition of 2-cyclohexene-1-hydroperoxide accelerated the rate of cyclohexene oxidation.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Ignacio Sancho, Marta Navarro, Marc Montilla, Pedro Salvador, Cristina Santamaria, Josep M. Luis, Alberto Hernan-Gomez
Summary: In this study, a detailed route for the formation of titanium(III) orthophenylendiamido (PDA) species using [LiBHEt3] as a reducing agent is provided. These low-valent compounds in combination with [PPN]Cl are highly selective catalysts for the copolymerization of CO2 and cyclohexene epoxide.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yunzhou Chen, Huatian Shi, Chi-Sing Lee, Shek-Man Yiu, Wai-Lun Man, Tai-Chu Lau
Summary: The study introduces a new series of cobalt complexes that function as efficient catalysts for aerobic peroxidation of hydrocarbons at room temperature, offering a potential solution to the challenge of room temperature aerobic oxidation of hydrocarbons.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Mengjun Gong, Yanjun Guo, Daniel Malko, Javier Rubio-Garcia, Jack M. S. Dawson, George J. P. Britovsek, Anthony Kucernak
Summary: Under mild conditions, aldehydes are efficiently converted to epoxides using a heterogeneous Fe-N/C catalyst, which forms the corresponding organic peroxy acid and acylperoxy radicals. Real-time monitoring of oxygen consumption and catalyst potential reveals the formation of peroxy acid and subsequent catalytic epoxidation. The involvement of aldehyde and Fe-N/C catalyst is shown to be the rate determining step for the reaction, and the induction time can be increased by adding a radical scavenger.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Tingting Ma, Chao Xu, Fengyang Liu, Yirong Feng, Wenyan Zhang, Weiwei Tang, Haoyu Zhang, Xiaowei Li, Yingying Nie, Shuangfei Zhao, Yuguang Li, Dong Ji, Zheng Fang, Wei He, Kai Guo
Summary: Selective epoxidation and allylic oxidation of cyclohexene were achieved using BEA-Ti and (metallo)porphyrin catalysts. The combination of BEA-Ti and porphyrin H2MTPP resulted in high selectivity for cyclohexene oxide. BEA-Ti and metalloporphyrin MnMTPP yielded high selectivity for 2-cyclohexen-1-one. The oxidation process was promoted by active species involving (metallo)porphyrin, TiIV sites, and TBHP, and an improved outer-sphere effect on the surface of BEA-Ti framework contributed to enhanced conversion and selectivity in epoxidation and allylic oxidation.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Tanmoy Pain, Ajit Kumar Singh, Arup Tarai, Sruti Mondal, Arindam Indra, Sanjib Kar
Summary: A new class of antimony(III) corroles with altered photophysical properties have been synthesized, which show potential for electrocatalysis.
INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Xiaodong Li, Ailing Feng, Yanqing Zu, Peitao Liu, Fengbo Han
Summary: Modifying non-precious metal porphyrins at the meso-position improves the activation of O-2 and the selectivity of redox products. By replacing FeTPPCl with a crown ether-appended Fe(III) porphyrin complex (FeTC4PCl), the reactions of FeTPPCl and FeTC4PCl catalysed by O-2 oxidation of cyclohexene were studied. The mechanism of the cyclohexene oxidation reaction with FeTC4PCl as a catalyst and O-2 as an oxidant was deduced as a free radical chain reaction process.
Article
Chemistry, Organic
Xu Zhang, Xuefeng Xu, Yue Shi, Di Wang, Yanhua Ding, Shuyang Chen
Summary: Cobalt(III)-catalyzed allylation of 1,3-dicarbonyl compounds has been achieved using in situ generated allyl reagents from alkenes and dimethyl sulfoxide (DMSO). This novel protocol allows for the selective synthesis of a wide range of allyl 1,3-dicarbonyl compounds. DMSO serves as a C1 source in the reaction and reacts with alkenes to form the allyl reagent allylic methyl thioether. Additionally, a proposed multiple-step pathway involving silver-mediated coupling, Co(III)-catalyzed pi-allylation, and intermolecular nucleophilic substitution rationalizes the mechanism study.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Jemal M. Yassin, Abi M. Taddesse, Manuel Sanchez-Sanchez
Summary: Ti-MOFs have significant research and industrial demand due to their extraordinary photocatalytic potential. In this study, a new Ti-MOF was presented under sustainable conditions and novel Ti-BDC based ternary photocatalysts were successfully prepared, showing high photocatalytic performance and stability.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Ramon de la Serna, David Nieto, Raquel Sainz, Beatriz Bernardo-Maestro, Alvaro Mayoral, Carlos Marquez-Alvarez, Joaquin Perez-Pariente, Luis Gomez-Hortiguela
Summary: Scientists reported the discovery of a new type of chiral zeolite material, GTM-3, with extra-large pores. This material demonstrated excellent enantioselectivity and the ability to catalyze reactions with bulky substrates. The researchers achieved unprecedented product enantiomeric excesses of up to 30% by catalyzing the epoxide aperture of transstilbene oxide with alcohols. This discovery opens new possibilities for the catalytic asymmetric synthesis of chiral pharmaceutical compounds using chiral zeolite materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Mercedes Boronat, Maria J. Climent, Patricia Concepcion, Urbano Diaz, Hermenegildo Garcia, Sara Iborra, Antonio Leyva-Perez, Lichen Liu, Agustin Martinez, Cristina Martinez, Manuel Moliner, Joaquin Perez-Pariente, Fernando Rey, Enrique Sastre, Pedro Serna, Susana Valencia
Summary: This article introduces the significant contributions of Prof. Avelino Corma in the field of heterogeneous catalysis and materials science. It highlights his remarkable achievements in areas such as solid catalysts, materials synthesis, and photochemistry. The article also emphasizes the importance of the research methods and paradigms developed by Avelino and his team in addressing new scientific challenges in building a sustainable world.
Article
Chemistry, Physical
Misael Garcia Ruiz, Dora A. Solis Casados, Julia Aguilar Pliego, Carlos Marquez Alvarez, Enrique Sastre de Andres
Summary: This study investigates the use of zeolitic catalysts and modified zeotypes for the transformation of methanol to hydrocarbons (MTH). It was found that the incorporation of zinc in ZSM-5 zeolite had a significant impact on acidity and increased selectivity to BTX fraction. Additionally, the modified commercial zeolite with zinc ions exhibited complete conversion of methanol with higher selectivity to aromatic compounds.
Article
Chemistry, Multidisciplinary
Mitin Belaye, Abi M. Taddesse, Endale Teju, Manuel Sanchez-Sanchez, Jemal M. Yassin
Summary: This study aimed to investigate the adsorption efficiency of Ce(III)-BDC metal-organic framework (MOF) for the removal of phosphate and fluoride ions from aqueous solution. The experimental results showed that the MOF exhibited outstanding removal efficiency for these ions under optimized conditions, and that SO4 (2-) and PO4 (3-) ions were the primary interfering ions for phosphate and fluoride adsorption, respectively.
Article
Chemistry, Multidisciplinary
Rafael Delgado, Carlos Marquez-Alvarez, Alvaro Mayoral, Ramon de la Serna, Javier Agundez, Joaquin Perez-Pariente
Summary: Gold nanospecies immobilized on functionalized mesoporous silica were tested as catalysts for cyclohexene oxidation. The materials were compared with previously reported ones functionalized during synthesis. Catalytic tests under different conditions were carried out and the samples were characterized by various techniques. The catalysts showed lower activity than those supported on S-bearing SBA-15 functionalized in situ due to different ratios of gold to sulfur. The reaction was found to be photocatalyzed by in situ formed AuNPs under ambient illumination.
CHEMISTRY-SWITZERLAND
(2023)
Article
Chemistry, Physical
Ainhoa Oliden-Sanchez, Rebeca Sola-Llano, Joaquin Perez-Pariente, Luis Gomez-Hortiguela, Virginia Martinez-Martinez
Summary: The combination of photoactive molecules and inorganic structures is important for the development of advanced materials in optics. In this study, bulky dyes were successfully encapsulated in a zeolitic framework, resulting in emission throughout the visible spectrum.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2024)
Article
Chemistry, Applied
Ramon de la Serna, Joaquin Perez-Pariente, Luis Gomez-Hortigueela
Summary: In this study, the asymmetric catalytic activity of GTM-3 chiral zeolite in the ring-opening reaction of trans-stilbene oxide using alcohols as nucleophiles was systematically explored. The results showed that a proper chiral host-guest size match is crucial for the chiral manifestation of the zeolite catalyst. Additionally, secondary alcohols with larger size exhibited higher enantioselectivity than their linear counterparts. Furthermore, variation of reaction conditions, such as the concentration of the epoxide and reaction temperature, could greatly influence the enantioselectivity and selectivity of the reaction.
Article
Chemistry, Applied
Alejandro Vidal de la Fuente, Amel Mekki, Bouhadjar Boukoussa, Marisol Grande-Casas, Enrique Sastre, Carlos Marquez-Alvarez, Manuel Sanchez-Sanchez, Joaquin Perez-Pariente
Summary: In this study, large-pore zeolite omega was treated with CTA to generate intracrystalline mesoporosity. The samples were characterized and it was found that dealumination and mild acid leaching are necessary for the formation of narrow-pore-diameter mesopores. The presence of mesopores enhances catalytic activity but does not improve selectivity.
Article
Chemistry, Multidisciplinary
Ramon de la Serna, Itziar Arnaiz, Carlos Marquez-Alvarez, Joaquin Perez-Pariente, Luis Gomez-Hortiguela
Summary: The chirality of the -ITV zeolite framework undergoes a surprising inversion when the ethyl group of the enantiopure N,N-ethyl-methyl-pseudoephedrinium organic structure-directing agent is replaced by a benzyl or 2-methylbenzyl group. Interestingly, chiral zeolite materials obtained with these new benzyl-containing cations exhibit unprecedentedly high enantiomeric excesses up to 55%.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Eddy Dib, Beatriz Bernardo-Maestro, Fernando Lopez-Arbeloa, Joaquin Perez-Pariente, Luis Gomez-Hortiguela
Summary: In this study, high-resolution H-1 MAS NMR was used to distinguish between two aggregation states of (1R,2S)-ephedrine occluded within AFI-type microporous aluminophosphates. The investigation focused on the supramolecular assembly of ephedrine molecules and the distances between aromatic rings and their closest protons inside the zeolite channels. The combination of two-dimensional spin diffusion spectra, molecular simulations, and DFT calculations allowed for precise estimation of these distances.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Applied
Qingyuan Zheng, Jack H. Williams, Scott Elgersma, Mick D. Mantle, Andrew J. Sederman, G. Leendert Bezemer, Constant M. Guedon, Lynn F. Gladden
Summary: In this study, a pilot-scale fixed-bed reactor compatible with NMR/MRI was developed for Fischer-Tropsch synthesis. Multiple magnetic resonance techniques were applied to quantitatively characterize different product species within catalyst pellets, providing valuable information for catalyst and reactor optimization.
Article
Chemistry, Applied
Lisa Ramisch, Sebastian Pfaff, Sabrina M. Gericke, Edvin Lundgren, Johan Zetterberg
Summary: We present a combination of optical operando techniques that allow simultaneous measurement of adsorbed species on catalyst surfaces, monitoring of surface oxide formation, and imaging of the gas phase above the catalyst surface. The experimental setup was validated by studying CO oxidation on Pd(100) at different pressures, revealing the effects of pressure on the heterogeneous catalytic reaction.
Article
Chemistry, Applied
Marta Paniagua, Gabriel Morales, Juan A. Melero, Daniel Garcia-Salgado
Summary: The influence of common impurities in levulinic acid on the catalytic performance of different acid catalysts for bio-jet fuel production was studied. It was found that furfural had the greatest detrimental effect on catalyst performance, while propyl-sulfonic acid-modified SBA-15 and sulfonic acid resin Amberlyst-70 showed good regeneration ability.
Article
Chemistry, Applied
Jesus Tapiador, Pedro Leo, Guillermo Calleja, Gisela Orcajo
Summary: This study presents a new MOF material, Zn-URJC-13, with acid and basic sites, permanent porosity, and high affinity to CO2 molecules. The Zn-URJC-13 catalyst exhibits efficient performance in CO2 cycloaddition reactions and can be reused multiple times.
Article
Chemistry, Applied
Dan Zhao, Vita A. Kondratenko, Dmitry E. Doronkin, Shanlei Han, Jan-Dierk Grunwaldt, Uwe Rodemerck, David Linke, Evgenii V. Kondratenko
Summary: This study demonstrates the potential of cheap and commercially available Zr or Ti-based supports and ZnO to serve as active and selective catalysts for propane dehydrogenation (PDH). The catalytically active species formed in situ under PDH conditions consist of isolated ZnOx. ZnOx on the surface of LaZrOx shows the highest rate of propene formation.
Article
Chemistry, Applied
Hanbyeol Kim, Jung Rae Kim, Young-Kwon Park, Jeong-Myeong Ha, Jungho Jae
Summary: In this study, metal phosphates were used as catalysts for biomass conversion to produce sustainable aromatics through DielsAlder cycloaddition reactions. The effects of synthesis method, activation method, and P/Ti molar ratio on the structure and acid properties of titanium phosphate catalysts were systematically studied. The mesoporous titanium phosphate catalyst synthesized by hydrothermal method at 180℃ for 12 h followed by ethanol refluxing at 60℃ for 24 h at a molar P/Ti ratio of 1 showed the highest surface area and acid site density.
Article
Chemistry, Applied
Yasin Khani, Sumin Pyo, Kwang-Eun Jeong, Chul-Ung Kim, Moonis Ali Khan, Byong-Hun Jeon, Kun-Yi Andrew Lin, Siyoung Q. Choi, Young-Kwon Park
Summary: A protonated form of Zeolite Socony Mobil-5 (H-ZSM-5) catalyst was synthesized through a hydrothermal method using different sources of silica. The effect of loading the catalyst with yttrium, samarium, and gadolinium on the acidic properties was investigated. Among the metal-loaded catalysts, the Sm/LHZ catalyst showed the best performance in the methanol to propylene conversion due to its high amount of weak and intermediate acid sites, while the Gd-LHZ catalyst increased the selectivity towards ethane and propane.
Article
Chemistry, Applied
Michael Franc, Ivana Cisarova, Jan Vesely
Summary: The present study investigates an enantioselective cyclization of enals with imidazolone derivatives catalyzed by a combination of achiral Pd(0) complex and chiral secondary amine. Corresponding spirocyclic imidazolones were produced in high yields with moderate diastereoselectivity and excellent enantioselectivity. The developed co-operative catalytic methodology provides a highly substituted spirocyclic scaffold with four stereogenic centers under mild conditions.
Article
Chemistry, Applied
Mauro Alvarez, Jennifer Cueto, David P. Serrano, Pablo Marin, Salvador Ordonez
Summary: This study focuses on improving the formulation and preparation methods of catalysts for the production of dimethyl carbonate. By using suitable catalyst preparation methods and copper salt precursors, the researchers successfully produced catalysts with optimal performance for dimethyl carbonate formation.
Article
Chemistry, Applied
Claudia J. Keijzer, Luc C. J. Smulders, Dennie Wezendonk, Jan Willem de Rijk, Petra E. de Jongh
Summary: This study investigates the catalytic behavior of alpha-alumina supported silver catalysts in the presence of chloride. It is found that the particle size of silver can affect the selectivity of the catalyst, but different strategies lead to different results. In this size range, the selectivity of ethylene oxide is correlated to the Ag : Al2O3 surface ratio.
Article
Chemistry, Applied
Takeshi Aihara, Wataru Aoki, Michikazu Hara, Keigo Kamata
Summary: The development of acid-base bifunctional catalysts is important for promoting specific chemical transformations. In this study, Ti-based perovskite oxides were synthesized and used as catalysts for two C-C bond-forming reactions (cyanosilylation and Knoevenagel condensation). The highly pure SrTiO3 nanoparticles with a high specific surface area exhibited the highest catalytic performance, and could be easily recovered and reused.
Article
Chemistry, Applied
Olga Gorlova, Petra Pribylova, Eliska Vyskocilova, Katerina Peroutkova, Jan Kohout, Iva Paterova
Summary: This study investigates the Baeyer-Villiger oxidation of beta-cyclocitral using tin-modified mixed oxides as catalysts. The optimal reaction conditions and the effects of various factors on the reaction course and selectivity were determined. The results show that tin-modified mixed oxides exhibit high activity and selectivity in the oxidation reaction.
Article
Chemistry, Applied
M. I. Avila, M. M. Alonso-Doncel, L. Briones, G. Gomez-Pozuelo, J. M. Escola, D. P. Serrano, A. Peral, J. A. Botas
Summary: The catalytic fast pyrolysis of lignin using ion-exchanged zeolite catalysts showed significant improvements in bio-oil quality and the production of aromatic hydrocarbons and oxygenated compounds.
Article
Chemistry, Applied
Enrico Catizzone, Giorgia Ferrarelli, Paolo Bruno, Girolamo Giordano, Massimo Migliori
Summary: The acid-catalysed alcohol conversion reaction is a promising route for de-fossilization strategies. Research on pure alcohol conversion and simultaneous dehydration of mixed alcohols have shown different product compositions, with the type and distribution of acid sites affecting the reaction mechanism.
Article
Chemistry, Applied
Alireza Ranjbari, Juho Kim, Jihee Yu, Jiyun Kim, Mireu Park, Nayoung Kim, Kristof Demeestere, Philippe M. Heynderickx
Summary: This study investigated a novel kinetic model for the adsorption and photocatalytic degradation of methyl orange using commercial ZnO and reduced ZnO photocatalysts. The results provided new insights into the interaction of catalysts with molecules of different charges and compared with a previous study on methylene blue. The presence of oxygen vacancies in ZnO and their effects on adsorption and photocatalytic degradation were analyzed, and the photocatalytic degradation rate of reduced ZnO was found to increase significantly.