Article
Chemistry, Multidisciplinary
Xian-Tai Zhou, Hai-Yang Yu, Yang Li, Hai-Bo Wu, Hong-Bing Ji
Summary: This work achieved the aerobic epoxidation of propylene catalyzed by manganese porphyrins in the presence of isoprene. The conversion of propylene was 38% with a selectivity toward propylene oxide (PO) up to 87%. The role of isoprene was demonstrated, and a plausible mechanism was proposed. The study is expected to provide a strategy for the simultaneous preparation of propylene oxide and isoprene monoxide.
CHINESE CHEMICAL LETTERS
(2023)
Article
Engineering, Chemical
Xian-Tai Zhou, Ling-Ling Wang, Yang Li, Hong-Bing Ji
Summary: In this study, a direct liquid-phase propylene aerobic epoxidation protocol using chloride manganese meso-tetraphenylporphyrin catalyst was developed. The conversion of propylene reached 12.3%, and the selectivity towards propylene oxide was 80.5%. It was confirmed that the formation of propylene oxide occurred via high-valent manganese species.
CHINESE JOURNAL OF CHEMICAL ENGINEERING
(2022)
Article
Chemistry, Physical
Yuhua Zheng, Mitsutaka Okumura, Xiaoyue Hua, Ayaka Sonoura, Huijuan Su, Hiroki Nobutou, Xun Sun, Libo Sun, Fengshou Xiao, Caixia Qi
Summary: Different ZrO2 phases were used as carriers for gold nanoparticles in the production of propylene oxide. Both tetragonal and monoclinic ZrO2 supports showed 100% selectivity to PO with similar nanogold dispersion, but the effects on PO formation differed between the two supports.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Chao Xiong, Yaorong He, Dejing Xu, Xiaohui Liu, Can Xue, Xiantai Zhou, Hongbing Ji
Summary: Activation of inert propylene to produce propylene oxide (PO) is crucial, and a temperature-controlled phase transfer catalyst MoOO.DMF has been prepared for efficient epoxidation. The catalyst exhibits high selectivity and productivity for PO, and can be dissolved in solvent at higher temperatures and separated after reaction. The mechanisms have been proved by in-situ FT-IR, ESR and HRMS spectrum, showing the selective oxygen transfer from tertbutyl peroxide radical and Mo-O-O bridge in MoOO.DMF.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Nidhi Kapil, Tobias Weissenberger, Fabio Cardinale, Panagiotis Trogadas, T. Alexander Nijhuis, Michael M. Nigra, Marc-Olivier Coppens
Summary: This study presents a facile method for synthesizing a stable Au/TS-1 catalyst, which shows improved catalytic performance in direct gas phase epoxidation compared to traditional methods. Various characterization techniques illustrate the structure-stability relationship of the catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
William N. Porter, Zhexi Lin, Jingguang G. Chen
Summary: This review summarizes experimental and theoretical studies on model catalysts for propylene epoxidation, focusing on methods for improving PO selectivity and the application of density functional theory in studying reaction mechanisms.
SURFACE SCIENCE REPORTS
(2021)
Article
Chemistry, Physical
Wenqian Li, Longfei Chen, Minghuang Qiu, Wanting Li, Yanfei Zhang, Yanfeng Zhu, Jiong Li, Xinqing Chen
Summary: In this study, a non-noble Ni/TS-1 catalyst was developed and shown to exhibit high catalytic performance in the gas-phase epoxidation of propylene. The performance of this catalyst was even better than that of the gold-based catalyst, and it provides a promising approach for the efficient oxidation reaction with non-noble metals.
Article
Chemistry, Physical
Joseph Esposito, Aditya Bhan
Summary: Selective propylene epoxidation can be promoted by surface-bound chlorine adatoms (Cl*) on K-promoted Ag/CaCO3 catalysts. The presence of gaseous promoters (NO, CO2, and C2H5Cl) and propylene oxychlorination lead to the formation of highly unstable allyl chloride intermediate, which controls Cl* coverages and induces significant bed-scale Cl* gradients during propylene epoxidation. The control of Cl* coverages by in situ generated allyl chloride is highly consequential for selective epoxidation, resulting in increased epoxide selectivity and site-time yield as propylene conversion increases.
Article
Chemistry, Physical
Michael B. Burkholder, Masudur Rahman, Arthur C. Reber, Anne M. Gaffney, B. Frank Gupton, John R. Monnier
Summary: A series of Ag-based catalysts were studied for direct epoxidation of propylene using molecular O2 as the oxidant. Different supports, Ag loadings, and feed additives were investigated to optimize catalyst performance. The results showed that adding ethyl chloride inhibited consecutive oxidation reactions, while nitric oxide increased activity. High loadings of K+ promoter were essential to stabilize both chlorine and nitric oxide on the catalyst surface. PO selectivities as high as 50% were achieved.
APPLIED CATALYSIS A-GENERAL
(2023)
Article
Chemistry, Applied
Kang Tang, Weilong Hou, Xiaoshu Wang, Wen Xu, Xinqing Lu, Rui Ma, Yanghe Fu, Weidong Zhu
Summary: The trimethylsilylated TiMWW zeolite, Si-Ti-MWW, is developed as a catalyst for the HPPO process, showing higher selectivity and stability by effectively inhibiting the solvolysis of PO to byproducts.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Chemistry, Physical
Wei Du, Zhihua Zhang, Yanqiang Tang, Qianhong Wang, Nan Song, Xuezhi Duan, Xinggui Zhou
Summary: In this study, it was found that the proportion of Ti sites in close proximity to Au is smaller compared to Ti sites away from Au. The remote Ti sites were proposed to catalyze PO formation through a tandem mechanism with the help of active oxidant species migration. The kinetic behaviors were found to be connected with the catalyst structure, providing guidance for designing efficient tandem catalysts for the HOPO process.
Article
Chemistry, Physical
Emilia A. Carbonio, Frederic Sulzmann, Alexander Yu. Klyushin, Michael Haevecker, Simone Piccinin, Axel Knop-Gericke, Robert Schloegl, Travis E. Jones
Summary: The development of catalysts for direct epoxidation of propylene to produce propylene oxide using oxygen is challenging. The low selectivity over silver catalysts is attributed to the lack of electrophilic oxygen. The addition of electrophilic-O via SO4 oxyanions and Cl activation of the oxyanion can significantly increase the selectivity to propylene oxide.
Article
Chemistry, Physical
Zixuan Yang, Huijuan Su, Yanan Cheng, Xun Sun, Libo Sun, Lijun Zhao, Caixia Qi
Summary: This study investigates the gas-phase epoxidation of propylene using as-synthesized TS-1 catalyst with a small amount of anatase TiO2. The addition of metallic Au and calcination in O-2 are found to improve the catalytic performance of Au/TS-1. It is also observed that more acrolein is produced when the catalyst is calcined in O-2 compared to H-2.
Article
Chemistry, Physical
Jeremy W. Arvay, Wei Hong, Christina Li, Fabio H. Ribeiro, W. Nicholas Delgass, James W. Harris
Summary: The catalytic roles of extracrystalline and intracrystalline gold nanoparticles on the direct propylene epoxidation were investigated, and it was found that there was no intrinsic difference between the two. The kinetics of the reaction were measured and the results were consistent with previous studies on intracrystalline gold nanoparticles. An active site model was developed and the estimated turnover frequencies were 20 times higher than previous estimates. The dispersion of gold was found to affect the rate of hydrogen oxidation.
Article
Chemistry, Physical
Jeremy W. Arvay, Wei Hong, Christina Li, W. Nicholas Delgass, Fabio H. Ribeiro, James W. Harris
Summary: In this study, the difference in catalytic roles of extracrystalline and intracrystalline gold nanoparticles in direct propylene epoxidation was investigated. The results showed that the activation energy and reaction orders for propylene epoxidation were similar for both types of nanoparticles. However, the activation energy for hydrogen oxidation differed, indicating a change in rate-limiting step or active site. An active site model was developed to estimate catalytic turnover frequencies and it was found that the simultaneous mechanism occurring over proximal Au-Ti sites alone is not sufficient to explain the observed rate of propylene epoxidation, suggesting the kinetically relevant short-range migration of hydrogen peroxide. The study also found that the rates of hydrogen oxidation varied proportionally to the amount of surface gold atoms, indicating the importance of gold dispersion in the catalysts.
Article
Chemistry, Physical
Beatriz Martinez-Sanchez, Javier Quilez-Bermejo, Emilio San-Fabian, Diego Cazorla-Amoros, Emilia Morallon
Summary: Electrochemical functionalization of single-walled carbon nanotubes and herringbone carbon nanotubes (SWCNTs and hCNTs, respectively) with aminophenylphosphonic acid isomers has been successfully achieved. Selectivity and control of the functional species incorporated into the carbon nanotubes were accomplished by optimizing the electrochemical conditions. X-ray photoelectron spectroscopy (XPS) analysis revealed the maximum heteroatom incorporation of nitrogen and phosphorus in the carbon materials. The study also explored the role of SWCNT and hCNT structures in the functionalization process.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
Review
Biochemistry & Molecular Biology
Roberto Morellon-Sterling, Olga Tavano, Juan M. Bolivar, Angel Berenguer-Murcia, Gilber Vela-Gutierrez, Jamal S. M. Sabir, Veymar G. Tacias-Pascacio, Roberto Fernandez-Lafuente
Summary: This article highlights the complexities of immobilizing pepsin and discusses potential methods and applications. The lack of primary amino groups on the enzyme's surface and its poor stability at alkaline pH values present challenges for immobilization. The review also proposes possibilities for achieving both covalent immobilization and stabilization of pepsin through multipoint covalent attachment.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2022)
Article
Energy & Fuels
Jessica Chaparro-Garnica, Miriam Navlani-Garcia, David Salinas-Torres, Angel Berenguer-Murcia, Emilia Morallon, Diego Cazorla-Amoros
Summary: In this study, Pd-based biomass-derived carbon-supported catalysts were developed using a simple method. The effects of modifying the metal phase and support, as well as the synthetic protocol used, were assessed. It was found that the resulting PdAg-based catalysts supported on N-doped biomass-derived carbon materials exhibited suitable activity and excellent stability under reaction conditions.
Article
Environmental Sciences
J. X. Flores-Lasluisa, F. Huerta, D. Cazorla-Amoros, E. Morallon
Summary: Transition metal oxide-based materials are interesting alternatives to noble-metal catalysts in energy conversion devices. Perovskite and spinel oxides can be tailored to have specific properties. However, their catalytic performance is affected by low electrical conductivity and surface area, which can be mitigated by combining them with carbon materials. This review focuses on tunable perovskites and spinels with 3d metal cations for electrochemical energy conversion.
ENVIRONMENTAL RESEARCH
(2022)
Article
Biochemistry & Molecular Biology
Daniel Castaneda-Valbuena, Angel Berenguer-Murcia, Roberto Fernandez-Lafuente, Roberto Morellon-Sterling, Veymar G. Tacias-Pascacio
Summary: The fishing industry generates valuable waste that contains a high amount of proteins. Processing these proteins can lead to products with nutritional, pharmacological, and technological benefits due to the presence of peptides. This review compiles investigations on the production of peptides from fish proteins using pepsin as a catalyst, highlighting their biological properties and potential uses.
PROCESS BIOCHEMISTRY
(2022)
Article
Chemistry, Physical
M. Garcia-Rodriguez, J. X. Flores-Lasluisa, D. Cazorla-Amoros, E. Morallon
Summary: This study highlights the use of metal oxide perovskites mixed with carbon materials as promising electrocatalysts for Zn-air batteries. The mixing method, particularly ball-milling, was found to strongly influence the particle size and interaction between the components, leading to improved electrocatalytic activity. The optimized electrocatalysts displayed enhanced performance in oxygen reduction and evolution reactions, outperforming a commercial Pt/C electrocatalyst in terms of cyclability and energy density.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Physical
Alicia Trigueros-Sancho, Beatriz Martinez-Sanchez, Diego Cazorla-Amoros, Emilia Morallon
Summary: One-step dry ball-milling method was used to prepare different electrocatalysts based on cobalt(II) or iron(II) phthalocyanines supported on commercial carbon materials, without the need for pre-treatment, solvent addition, or post-processing steps. The as-prepared catalysts exhibited improved electrocatalytic performance, and the FePc supported on CNovel showed excellent activity for oxygen reduction reaction in alkaline medium. This study provides a simple and cost-effective approach for catalyst manufacturing through mechanochemistry.
Article
Electrochemistry
Gabriel Alemany-Molina, Beatriz Martinez-Sanchez, Atsushi Gabe, Takeshi Kondo, Diego Cazorla-Amoros, Emilia Morallon
Summary: The interest in conductive boron-doped diamond powder (BDDP) electrodes has increased due to their stability, wide potential window, large specific surface area, and versatility. They are proposed as alternative cathode catalyst supports in fuel cells, especially in automobiles. In this study, different BDDP supports were used with different particle sizes and surface oxygen contents to support different iron species for oxygen reduction reaction. The electrocatalytic performance was influenced by the surface chemistry of the BDDP supports for FePc samples, while the particle size of the BDDP support played a determining role for Fe-C3N4 samples. DFT calculations provided insights into the interaction of FePc with the diamond surface.
ELECTROCHIMICA ACTA
(2023)
Article
Thermodynamics
J. X. Flores-Lasluisa, F. Huerta, D. Cazorla-Amoros, E. Morallon
Summary: LaNi1-xCoxO3 perovskite materials were synthesized for electrochemical reactions involving molecular oxygen. Incorporation of Co induced changes in material surface and improved electrocatalytic activity. Mixing perovskite metal oxides with carbon black enhanced electron transfer and catalytic activity. LaNi0.5Co0.5O3/Vulcan showed high stability and was a suitable bifunctional catalyst for both ORR and OER.
Article
Chemistry, Physical
M. E. Sandoval-Salinas, R. Bernabeu-Cabanero, A. J. Perez-Jimenez, E. San-Fabian, J. C. Sancho-Garcia
Summary: We theoretically study a series of rhombus-shaped nanographenes of increasing size, called n-rhombenes, which exhibit zigzag edges leading to enhanced radicaloid properties and intrinsic magnetism. We use spin-flip methods to capture the challenging physics of the problem and provide accurate energy differences between high- and low-spin solutions. The theoretical predictions are in agreement with experimental data and reveal the transition from a closed-shell to an open-shell ground-state solution.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Meeting Abstract
Chemistry, Physical
Gabriel Alemany-Molina, Beatriz Martinez-Sanchez, Emilia Morallon, Diego Cazorla-Amoros
Article
Chemistry, Multidisciplinary
Cristian Daniel Jaimes-Paez, Francisco Jose Garcia-Mateos, Ramiro Ruiz-Rosas, Jose Rodriguez-Mirasol, Tomas Cordero, Emilia Morallon, Diego Cazorla-Amoros
Summary: The aim of this study is to determine the Oxygen Reduction Reaction (ORR) activity of self-standing electrospun carbon fiber catalysts obtained from different metallic salt/lignin solutions. Carbon fibers were prepared by electrospinning technique with metallic nanoparticles (Co, Fe, Pt, and Pd) embedded in organosolv lignin. The presence of metals resulted in increased porosity during carbonization, leading to improved accessibility of the electrolyte to active sites. Carbon fibers loaded with 8 wt% palladium showed the best ORR activity with superior dispersion and balanced pore size distribution.
Review
Chemistry, Multidisciplinary
Jose Renato Guimaraes, Kaique Souza Goncalves Cordeiro Oliveira, Maria Carolina Pereira Goncalves, Joao Paulo Romanelli, Laiane Antunes Lopes, Angel Berenguer-Murcia, Roberto Fernandez-Lafuente, Paulo Waldir Tardioli
Summary: This article reviews the research on the immobilization of lipases on hydrophobic supports using systematic mapping (SM) concepts. It covers a wide range of lipases and supports, discussing their advantages and highlighting issues related to the immobilization process. Strategies to overcome these issues, such as immobilization on heterofunctional supports or intermolecular crosslinking, are also discussed. The structure, distribution, and co-occurrence frequency of lipases and supports are analyzed to determine potential research hotspots and unexplored advances in knowledge.
REACTION CHEMISTRY & ENGINEERING
(2023)
Review
Chemistry, Multidisciplinary
Jose Renato Guimaraes, Kaique Souza Goncalves Cordeiro Oliveira, Maria Carolina Pereira Goncalves, Joao Paulo Romanelli, Laiane Antunes Lopes, Angel Berenguer-Murcia, Roberto Fernandez-Lafuente, Paulo Waldir Tardioli
Summary: This article presents a systematic review of literature on the immobilization of lipases on hydrophobic supports. The study identifies various lipases and supports used in the research, discusses the advantages of immobilization on hydrophobic supports, and highlights problems and strategies for overcoming them.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Yifan Sun, Ye Lv, Wei Li, Jinli Zhang, Yan Fu
Summary: In this study, PtRu electrocatalysts were fabricated on carbon paper via cyclic electrodeposition for the electrocatalytic hydrogenation (ECH) of phenol. The Pt3Ru3 catalyst exhibited excellent activity and stability for the conversion of phenol to cyclohexanol at ambient temperature and various current densities. The in situ Raman spectroscopy and kinetic study revealed the hydrogenation mechanism of phenol over Pt3Ru3 in acidic electrolyte, providing an effective electrochemical strategy for the facile construction of durable electrode materials and efficient phenol hydrogenation.
JOURNAL OF CATALYSIS
(2024)
Article
Chemistry, Physical
Amir Shahzad, Khezina Rafiq, Muhammad Zeeshan Abid, Naseem Ahmad Khan, Syed Shoaib Ahmad Shah, Raed H. Althomali, Abdul Rauf, Ejaz Hussain
Summary: Photocatalytic hydrogen production through water splitting is an effective method for meeting future energy demands. In this study, researchers synthesized a 1 % Ag2S/Cu2S co-doped CdZnS catalyst and found that it can produce hydrogen at a higher rate. The co-doping of Ag2S and Cu2S in the CdZnS catalyst showed a synergistic effect, with Ag2S promoting oxidation reactions and Cu2S promoting reduction reactions.
JOURNAL OF CATALYSIS
(2024)
