Article
Chemistry, Multidisciplinary
P. Rani, N. Pundir, Heena, A. Husain, A. K. K. Bhasin, K. K. Bhasin, G. Kumar
Summary: Two new doubly interpenetrated MOFs were studied and found to be effective in amino acid sensing and catalytic reactions.
MATERIALS TODAY CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sandra Albarracin-Suazo, Lucas Freitas de Lima e Freitas, Blake MacQueen, Andreas Heyden, Jochen A. Lauterbach, Eranda Nikolla, Yomaira J. Pagan-Torres
Summary: This study demonstrates the activity, selectivity, and stability of earth-abundant molybdenum oxide based heterogeneous catalysts for the cleavage of vicinal C-O bonds in biomass-derived polyols. By improving catalyst structure and stability, the conversion of biobased polyols to platform chemicals can be achieved.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Alessandro Messori, Giulia Martelli, Andrea Piazzi, Francesco Basile, Jacopo De Maron, Andrea Fasolini, Rita Mazzoni
Summary: Molecular ruthenium cyclopentadienone complexes were used as pre-catalysts in the homogeneously catalysed Aqueous Phase Reforming (APR) of glucose for the first time. Shvo's complex was identified as the best pre-catalyst (loading 2 mol%) with H-2 yields up to 28.9% at 150 degrees C. In situ NMR experiments and HPLC analyses revealed the presence of sorbitol, fructose, 5-hydroxymethylfurfural and furfural as final products or intermediates in the transformations under APR conditions. Benzoquinone was found to positively affect catalyst activation when used as an equimolar additive.
Article
Chemistry, Physical
Kosuke Yamaguchi, Yoshinao Nakagawa, Congcong Li, Mizuho Yabushita, Keiichi Tomishige
Summary: The removal of vicinal diols through deoxydehydration and hydrogenation reactions using a mixture catalyst of ReOx/CeO2 and CeO2-supported base metals has been studied as an alternative to the expensive Pd-based catalysts. The mixture catalyst showed high activity and selectivity similar to that of Pd-based catalysts, and could be applied to various diols and polyols. However, the activity of the mixture catalyst decreased during reuse.
Review
Chemistry, Multidisciplinary
Yuanyuan Yao, Yuqi Pan, Yanxi Yu, Zixun Yu, Leo Lai, Fangzhou Liu, Li Wei, Yuan Chen
Summary: This article reviews bifunctional catalysts for heterogeneous electro-Fenton processes. The generation mechanism of oxidizing radicals from oxygen is described, and different types of bifunctional catalysts are compared based on their elemental compositions. Additionally, five other methods beyond electrocatalysts that can improve the performance of heterogeneous electro-Fenton processes are presented.
ENVIRONMENTAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Fabian Lutz, Nerea Lorenzo-Parodi, Torsten C. Schmidt, Jochen Niemeyer
Summary: This study reports the self-assembly of bifunctional photoredoxcatalysts by functionalizing a series of photosensitizers and water-reducing catalysts with viologen- and naphthol-units, followed by the formation of heteroternary cucurbit[8]uril-viologen-naphthol complexes for hydrogen generation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Florian D'Ambra, Julia Levy, Parviz Hajiyev, Thibault Cantat, Vincent Faucheux, Emmanuel Nicolas
Summary: In this study, we propose a new biobased and bifunctional liquid organic hydrogen carrier (LOHC) consisting of 1-Cyclohexylethanol/Acetophenone. Experimental and simulation results demonstrate that this material can be efficiently hydrogenated and dehydrogenated with the commercial catalysts Ru/Al2O3 and Pt/C. The system shows good stability after multiple cycles and exhibits potential for high-capacity hydrogen storage.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Review
Engineering, Environmental
Mengzhu Li, Weinan Yin, Junan Pan, Yanwei Zhu, Ning Sun, Xinyu Zhang, Yingtong Wan, Zhongzhong Luo, Lanhua Yi, Longlu Wang
Summary: Hydrogen spillover, a phenomenon of active species migration, has received considerable attention in recent years. It not only participates in catalytic reactions as reactants, but also induces support to form defects or phase transitions, thereby adjusting the energy band and improving catalytic performance. As a result, hydrogen spillover has broad potential applications in heterogeneous catalysis and hydrogen production. However, there is still a lack of clear summary on the reaction mechanism and important applications of hydrogen spillover. This review focuses on the recent progress of hydrogen spillover, including different types, structural models, and applications, aiming to provide new ideas for the design and application of hydrogen spillover.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Ming Zhang, Xiao-Chen Wang
Summary: This method presents a mild and efficient approach for synthesizing enantioenriched tetrahydroquinoline-fused cyclobutenes through a cascade reaction, catalyzed by chiral spiro-bicyclic bisboranes. The bisboranes function by catalyzing hydride transfer and activating the alkynone substrate for an enantioselective cycloaddition reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Hao Tian, Yanling He, Qinglong Zhao, Jiaxin Li, Xiji Shao, Zhe Zhang, Xiang Huang, Chao Lu, Kedong Wang, Qichuan Jiang, A. M. C. Ng, Hu Xu, S. Y. Tong
Summary: The new strategy avoids conflicting tasks and enhances the efficiency of bifunctional catalysts by directly obtaining OH from water to facilitate CO conversion on a weakly reactive substrate.
Article
Chemistry, Physical
Yong Zhou, Martine Trentesaux, Maya Marinova, Sergei Chernyak, Jean-Charles Morin, Melanie Dubois, Samuel Eyley, Wim Thielemans, Vlad Martin-Diaconescu, Andrei Khodakov, Jeremie Zaffran, Vitaly Ordomsky
Summary: In conventional bifunctional catalysts, metal sites are responsible for catalytic activity, while acid sites are typically located on oxide supports. This study investigates the modification of metal sites with halogens to generate acidity through the heterolytic dissociation of hydrogen. High-throughput screening of different combinations of metals (Co, Ni, Ru, Pt, Pd, Rh) and halogens (Cl, Br, I) reveals that only Pd and Pt catalysts can form acid sites through interaction with Br, Cl, and I. Characterization and density functional theory (DFT) modeling suggest that hydrogen undergoes heterolytic dissociation over halogens located at the edges and corners of Pd and Pt nanoparticles, with the strength of the acid sites increasing with the electronegativity of the halogen.
Article
Chemistry, Physical
Yong Zhou, Martine Trentesaux, Maya Marinova, Sergei Chernyak, Jean-Charles Morin, Melanie Dubois, Samuel Eyley, Wim Thielemans, Vlad Martin-Diaconescu, Andrei Khodakov, Jeremie Zaffran, Vitaly Ordomsky
Summary: In conventional bifunctional catalysts, active metal sites are associated with metal components, while acid sites are usually localized over oxide supports. The modification of metal sites by halogens provides an opportunity to generate acidity via the heterolytic dissociation of hydrogen directly over metal sites. High-throughput screening of different metal-halogen combinations reveals that only Pd and Pt catalysts demonstrate the formation of acid sites by interaction with Br, Cl, and I. Characterization and density functional theory (DFT) modeling suggest that hydrogen heterolytic dissociation occurs over halogens localized at the edges and corners of Pd and Pt nanoparticles, with the strength of the acid sites increasing with the electronegativity of the halogen.
Article
Chemistry, Applied
Andreas Eitzinger, Jan Otevrel, Victoria Haider, Antonio Macchia, Antonio Massa, Kirill Faust, Bernhard Spingler, Albrecht Berkessel, Mario Waser
Summary: In this study, chiral 3,3-disubstituted isoindolinones were synthesized using ammonium salt catalysis, yielding a variety of differently substituted CF3S- and RS-derivatives with high enantioselectivities. Additionally, a racemic synthesis of F-containing products was achieved for the first time, producing a stable alpha-F-alpha-amino acid derivative.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Shitong Wang, Chengyi Wang, Ning Lv, Chunxia Tan, Tanyu Cheng, Guohua Liu
Summary: A yolk-shell-structured bifunctional magnetic catalyst was successfully prepared in this study, enabling efficient aerobic oxysulfonylation reactions of aryl-substituted terminal alkynes and asymmetric transfer hydrogenation to chiral beta-hydroxysulfones with high catalytic efficiency and enantioselectivity. Furthermore, this magnetic catalyst can be conveniently recovered and recycled via an additional outer magnet.
Article
Chemistry, Physical
Jianmei Cen, Liyan Wu, Yanfei Zeng, Asad Ali, Yuqing Zhu, Pei Kang Shen
Summary: This work demonstrates a viable approach for developing high catalytic performance of TMPs-based bifunctional electrocatalysts by designing and regulating the electronic structure and morphology of the catalyst. The designed NiFeCoP/NF nanorods exhibit excellent catalytic activities towards both OER and HER, achieving low overpotentials and outstanding stability in KOH solution. The water electrolysis device constructed with NiFeCoP/NF electrode as both the anode and cathode shows promising performance with low cell voltage.
Article
Chemistry, Physical
Youngchan Kim, Taehyup Kim, Ki Hyuk Kang, Insoo Ro
Summary: A series of TiO2-supported Pd catalysts with different amounts of ionic liquid (IL) were synthesized for selective hydrogenation. The Pd species in the catalysts exist mainly as isolated atoms on TiO2 independent of the presence of the IL. IL deposition induces a change in the electronic structure of atomically dispersed Pd atoms and improves the stability in acetylene hydrogenation due to their higher coke resistance.
Article
Chemistry, Physical
Jun Hee Jang, Jack T. Hopper, Insoo Ro, Phillip Christopher, Mahdi M. Abu-Omar
Summary: The study presents a one-step conversion of bioderived mucic acid to adipates using a heterogeneous, bifunctional Ir-ReOx/C catalyst. The catalyst with low Ir content enables reuse and regeneration for multiple cycles, providing a cost-effective option for the tandem deoxydehydration (DODH)-catalytic transfer hydrogenation (CTH) process. The reported system generates adipates in good yield without the need for additives or high pressure H-2, offering a sustainable and affordable route to manufacturing nylon and other polymers.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Zhexi Lin, Siddharth Deshpande, Steven R. Denny, William N. Porter, Cong Wang, Justin Marlowe, Phillip Christopher, Weiqing Zheng, Stavros Caratzoulas, Dionisios G. Vlachos, Jingguang G. Chen
Summary: This study investigates the reaction mechanism and active sites of THFA ring-opening on a WOx/Pt inverse oxide catalyst using model surface experiments, first-principles calculations, and catalyst characterization. The results demonstrate that the introduction of WOx can modulate the interaction strength between THFA and the surface, facilitating the desorption of the desired product. This study provides insights into catalyst design for the selective ring-opening of biomass-derived oxygenates.
Article
Chemistry, Physical
Gregory Zakem, Phillip Christopher
Summary: The study investigates the effect of active site mobility on reaction kinetics in heterogeneous catalysis. The researchers modified the mobility of atomically dispersed Rhodium on gamma-Al2O3 support and found that restricting mobility leads to lower desorption temperature and higher turnover frequency for a specific reaction. The analysis suggests that the changes in apparent activation entropy are responsible for the promoted rates. The study highlights the importance of active site entropy and controlling it for improving catalytic performance.
Article
Chemistry, Physical
Jordan Finzel, Kenzie M. Sanroman Gutierrez, Adam S. Hoffman, Joaquin Resasco, Phillip Christopher, Simon R. Bare
Summary: Single-atom catalysts (SACs) consisting of dispersed metal atoms have unique reactivity and efficient use of precious metals. X-ray absorption spectroscopy (XAS) is often used to identify metal species, but its limitations in detecting metal clusters have not been critically assessed. This article quantitatively assesses the detection limits of XAS and proposes a screening method using wavelet transform to differentiate atomically dispersed metal species and metal oxide clusters. The study provides best practices for studying SACs with XAS and emphasizes the importance of rigorous characterization.
Article
Chemistry, Multidisciplinary
Kamani Sudhir K. Reddy, Yi-Chun Chen, Ru-Jong Jeng, Mahdi M. M. Abu-Omar, Ching-Hsuan Lin
Summary: In this study, waste polycarbonate (WPC) was efficiently upcycled to poly-(carbonate imine) vitrimers (PCIs) with unprecedented acid resistance to 5 M H2SO4. The upcycling of WPC is essential for sustainability, and the acid resistance of PCIs expands their application in acidic environments. This environmentally friendly work will attract the attention of researchers interested in sustainability and circularity.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Baoyuan Liu, Zach Westman, Kelsey Richardson, Dingyuan Lim, Alan L. Stottlemyer, Thomas Farmer, Paul Gillis, Vojtech Vlcek, Phillip Christopher, Mahdi M. Abu -Omar
Summary: Polyurethane (PU) is a widely used plastic, with production reaching 24 million metric tons in 2018 and continuing to grow annually at 4%. However, the accumulation of PU waste poses a challenge for recycling due to its complex composition. Chemical recycling methods offer a potential solution, but there is a lack of understanding and commercial implementation of these methods. This article provides an overview of closed-loop chemical recycling methods for PU waste, focusing on the production of recycled polyol (repolyol) as a substitute for virgin polyol.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Engineering, Environmental
Huy Nguyen-Phu, Taeeun Kwon, Taehyup Kim, Lien Thi Do, Ki Hyuk Kang, Insoo Ro
Summary: By controlling the dispersion of Ru in Ru/SBA-15, the catalytic activity of LDPE hydrogenolysis can be improved. The addition of an optimal amount of TEA increases the dispersion of Ru species and enhances the hydrogen coverage, leading to higher yields in LDPE hydrogenolysis.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Environmental Sciences
Taehyup Kim, Huy Nguyen-Phu, Taeeun Kwon, Ki Hyuk Kang, Insoo Ro
Summary: In this study, a series of TiO2-supported Ru catalysts with different TiO2 crystalline phases were synthesized and used for the hydrogenolysis of polyethylene (PE). The results showed that the degree of strong metal-support interactions (SMSIs) varied depending on the type of TiO2 phase and reduction temperature, which influenced the catalysis of PE hydrogenolysis. Among the catalysts synthesized, Ru/TiO2 with the rutile phase (Ru/TiO2-R) exhibited the highest catalytic activity after high-temperature reduction, indicating the necessity of SMSIs for high activity in PE hydrogenolysis. Ru/TiO2-R could be successfully used for the hydrogenolysis of postconsumer plastic wastes, yielding valuable chemicals in high yields.
ENVIRONMENTAL POLLUTION
(2023)
Article
Chemistry, Physical
Jack T. Hopper, Ruining Ma, James B. Rawlings, Peter C. Ford, Mahdi M. Abu-Omar
Summary: In this study, a quantitative investigation was conducted on the liquid-phase dehydration of sorbitol using sulfated zirconia (SZ) solid acid catalysts synthesized via sol-gel method. The optimal catalyst achieved complete conversion of sorbitol to isosorbide in less than 2 hours with a yield of 76%. The quantitative kinetics and structure-reactivity studies provided insights into the factors affecting product yields and SZ catalyst activity.
Editorial Material
Chemistry, Physical
Phillip Christopher
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Jaeha Lee, Peter Tieu, Jordan Finzel, Wenjie Zang, Xingxu Yan, George Graham, Xiaoqing Pan, Phillip Christopher
Summary: The addition of platinum-group metals (PGMs, e.g., Pt) to CeO2 promotes the rate of redox surface reactions in heterogeneous catalysis. However, the mechanistic picture of PGM-promoted H-2 reactions on CeO2 surfaces in powder catalysts remains unclear. This study investigates the influence of Pt nanoclusters and single atoms on H-2 reactions on Pt/CeO2 powder catalysts using controlled catalyst synthesis and various experimental techniques. The results show that Pt can promote H-2 consumption rates even when existing on a small fraction of CeO2 particles, and Pt changes the activation mechanism and rate limiting step for H-2 on CeO2 surfaces.
Article
Engineering, Chemical
Emily K. Schroeder, Prasanna Dasari, Muhammad Amtiaz Nadeem, Dustin Fickel, Phillip Christopher
Summary: The activity and stability of bimetallic Pt-Ir nanoparticles supported on an Al2O3/ZSM-5 mixture were investigated for butane hydrogenolysis to ethane. A specific regeneration protocol involving the exposure of the oxidized catalyst to a butane and hydrogen mixture followed by post-reduction was identified to recover the catalyst activity and enhance its stability. Carefully designed pretreatment protocols that deposit stable adsorbates are presented as a valuable tool for controlling the surface composition of bimetallic nanoparticles and improving their catalytic performance.
ACS ENGINEERING AU
(2023)
Article
Chemistry, Multidisciplinary
Jun Hee Jang, Ana Rita C. Morais, Megan Browning, David G. Brandner, Jacob K. Kenny, Lisa M. Stanley, Renee M. Happs, Anjaneya S. Kovvali, Joshua I. Cutler, Yuriy Roman-Leshkov, James R. Bielenberg, Gregg T. Beckham
Summary: Many biomass conversion technologies focus on specific processing conditions for individual feedstocks, while neglecting the need for a practical operational window for processing a wide range of lignocellulosic biomass substrates. This study demonstrates the feedstock flexibility of reductive catalytic fractionation (RCF) in both batch and flow-through modes, effectively processing various biomass types (hardwoods, softwoods, and herbaceous monocots) regardless of their composition and structure differences. RCF with methanol as a solvent achieves high delignification and lignin monomer yields from different biomasses, while adding water as a co-solvent improves delignification values even further. The results indicate that RCF with an alcohol/water mixture can consistently handle a broad range of lignocellulosic biomasses.
