Article
Chemistry, Physical
Jachym Muck, Jaroslav Kocik, Martin Hajek, Zdenek Tisler, Karel Frolich, Ales Kasparek
Summary: This study focuses on the catalytic synthesis of butanol from ethanol in a microflow reactor. Different catalysts have varying effects on the formation of butanol and other products, with temperature increasing ethanol conversion but decreasing selectivity towards butanol.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Green & Sustainable Science & Technology
Karel Frolich, Jan Malina, Martin Hajek, Jachym Mueck, Jaroslav Kocik
Summary: The Guerbet reaction is an important way to transform ethanol to 1-butanol in various industries. This study focuses on the ethanol transformation using Mg-Al mixed oxides with copper or cobalt as catalysts in a microflow reactor. The results show that the series of catalysts containing copper exhibited higher conversion of ethanol and selectivity to butanol compared to the series containing cobalt. The study also verified a multi-step mechanism involving aldol condensation for both catalyst series and reaction conditions.
CLEAN TECHNOLOGIES AND ENVIRONMENTAL POLICY
(2023)
Article
Chemistry, Physical
Jie Li, Lu Lin, Yuan Tan, Shiyi Wang, Wenshao Yang, Xingkun Chen, Wenhao Luo, Yun-Jie Ding
Summary: The study prepared Cu/NiAlOx catalysts through hydrothermal precipitation method and found that Cu addition enhanced the reactivity in the conversion of ethanol into butanol. With sustained ethanol conversion of over 35% and butanol selectivity of around 45%, the catalyst exhibited excellent stability over time.
Article
Nanoscience & Nanotechnology
Sabrine M. Cypher, Magnus Pauly, Leslie G. Castro, Carrie L. Donley, Paul A. Maggard, Karen I. Goldberg
Summary: This study used a molecular catalyst integrated into a carbon nitride support to upgrade ethanol to n-butanol, which is one of the first examples of a supported molecular catalyst performing the Guerbet process. Initial studies using PTI with lithium or transition-metal cations imbedded in the support did not produce significant amounts of n-butanol. However, 59% selectivity for butanol (13% yield) was obtained at 145°C when using PTI-LiCl treated with [(Cp*)IrCl2] along with sodium hydroxide.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
P. M. Mahitha, S. Nakul, Naveen V. Kulkarni, Balaji R. Jagirdar, William D. Jones
Summary: A series of Ru(iii) complexes with accessible N-donor organic pincer ligands were used as catalysts in the Guerbet upgrading reaction of ethanol under aerobic conditions. The tridentate ligand systems with amino-dimethyl and pyridine backbones showed higher efficiency compared to the bidentate ligand systems with phenyl and ethene backbones. Potassium t-butoxide was the most compatible base for this catalyst system. A reaction with 0.1 mol% catalyst and 10 mol% potassium t-butoxide yielded 27% n-butanol at 71% selectivity (150 degrees C, 24 h).
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Izabela S. Pieta, Alicja Michalik, Elka Kraleva, Dusan Mrdenovic, Alicja Sek, Ewa Wahaczyk, Agnieszka Lewalska-Graczyk, Mikolaj Krysa, Anna Sroka-Bartnicka, Piotr Pieta, Robert Nowakowski, Agata Lew, Ewa M. Serwicka
Summary: The study focuses on fuel production methods from municipal solid wastes, with an emphasis on alcohol coupling to ethers. The synthesized samples play a crucial role in catalyst activity and product distribution, with multiple redox couples considered as the main active sites.
Article
Chemistry, Physical
Joachim Pasel, Johannes Haeusler, Dirk Schmitt, Helen Valencia, Joachim Mayer, Ralf Peters
Summary: The catalytic upgrading of CO2-based ethanol into valuable products, such as higher alcohols, is an increasingly popular research topic. Among these products, carbon-neutral n-butanol has the potential to replace a significant portion of conventional gasoline in the transportation sector. The Guerbet reaction, particularly the homo aldol condensation of acetaldehyde, has been studied as a promising synthesis route for n-butanol. In this study, the Temporal Analysis of Products methodology was used to investigate the reaction, with lanthanide oxides supported on activated carbon as catalysts. The research revealed the formation of butanol through the aldol condensation of acetaldehyde, as well as its decomposition into CO, CH4, and H2. Carbonaceous deposits were formed when acetaldehyde was pulsed onto the catalyst surface, but catalyst regeneration was successfully achieved through O2 pulsing. Other reaction routes leading to acidic acid, ethyl acetate, or diethyl ether were excluded through experimental tests.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Physical
J. Tyler Prillaman, Naomi Miyake, Robert J. Davis
Summary: The study investigated the catalytic conversion of ethanol to butanol and butadiene using calcium phosphate materials pretreated at different temperatures. Low temperature pretreatment resulted in high selectivity for acid-catalyzed products, while high temperature pretreatment led to the formation of coupling products.
Article
Chemistry, Physical
Richard L. Wingad, Laurence Birch, Joshua Farndon, Jason Lee, Katy J. Pellow, Duncan F. Wass
Summary: Ruthenium complexes with tetradentate PNNP donor ligands exhibit different selectivity in Guerbet catalysis compared to bis bidentate PN complexes, producing a mixture of n-butanol (17%), sec-butanol (14%) and ethyl acetate (66%) instead of the usual 90%+ selectivity to n-butanol. Tridentate PNP ruthenium complexes also produce sec-butanol and achieve 71% selectivity to this isomer in optimized conditions. The same tri- and tetradentate complexes are efficient catalysts for converting methanol/ethanol mixtures to isobutanol with up to 97% selectivity.
Article
Materials Science, Multidisciplinary
Andres A. Fragoso-Montes de Oca, J. G. Hernandez-Cortez, C. Angeles-Chavez, Jaime S. Valente, J. A. Toledo-Antonio
Summary: Cu/Zn/Al mixed oxide catalysts were synthesized from layered precursors, and the crystalline phase composition of the precursor determined the surface properties of the catalyst. Precursors mainly composed of HTLc phase resulted in a mixed oxide with high Lewis acidity and active hydro/dehydrogenation sites, while precursors mainly composed of Rosasite phase decomposed into Cu-0, ZnO, and Al2O3 during reduction, with Cu-0 acting as the dehydrogenation site.
MATERIALS CHEMISTRY AND PHYSICS
(2022)
Article
Chemistry, Applied
Zhinuo Wang, Ming Yin, Jifeng Pang, Xianquan Li, Yanan Xing, Yang Su, Shimin Liu, Xiaoyan Liu, Pengfei Wu, Mingyuan Zheng, Tao Zhang
Summary: In this study, Cu was selected to modify NiMgAlO catalysts for improving ethanol conversion and n-butanol selectivity. The optimized 2%Cu-NiMgAlO catalyst showed enhanced ethanol conversion and n-butanol selectivity in a 200-hour reaction time. The key role of multiple active sites in this reaction was extensively investigated.
JOURNAL OF ENERGY CHEMISTRY
(2022)
Article
Chemistry, Applied
S. Molina-Ramirez, M. Cortes-Reyes, C. Herrera, M. A. Larrubia, L. J. Alemany
Summary: New bifunctional catalysts were developed for the one-step synthesis of n-butanol, with Ca20Fe20MgAl-Ox achieving ethanol conversion rates of 36% at 280 degrees Celsius and 71% at 400 degrees Celsius, showing higher selectivity towards n-butanol and other C-4 compounds. The catalyst promotes the synthesis of C-4 compounds by modulating acid and basic sites, allowing ethanol to adsorb as ethoxy species and utilizing ethanol as a hydrogen donor.
Article
Chemistry, Multidisciplinary
R. Vinayagamoorthi, K. R. Krishnamurthy, B. Viswanathan, K. Shanthi
Summary: A new series of bimetallic Ni-Co catalysts have been evaluated for ethanol conversion to butanol and higher alcohols, showing better performance than mono metallic catalysts by step wise substitution of Ni with Co.
INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Applied
Anna Maria Raspolli Galletti, Claudia Antonetti, Sara Fulignati, Domenico Licursi, Stefano Dell'Omo, Patricia Benito, Erwin Wilbers, Hero Jan Heeres
Summary: The conversion of bio-alcohols to chemicals and fuels is crucial for the transition towards bioeconomy. Cu/Mg/Al mixed oxide catalysts derived from different hydrotalcites showed tunable catalytic performance in batch and continuous flow reactors for the conversion of nBuOH. Catalysts with lower Cu content exhibited activity in both Guerbet condensation and dehydrogenative coupling reactions, while the catalyst with the highest Cu content showed high selectivity towards butyl butyrate formation. Batch reaction showed gradual deactivation of the catalyst systems, while the study in flow reactor revealed good activity and stability of the Cu7.6 catalytic system.
Article
Chemistry, Inorganic & Nuclear
Anthony M. S. Pembere, Denis Magero, Godfrey O. Barasa, Gershom Kyalo Mutua, Hitler Louis, Haiming Wu
Summary: In this study, the mechanism of ethanol coupling to butanol over small metal clusters (copper, silver, and gold) was investigated. It was found that charge transfer interactions between the clusters and the alcohol play a crucial role in initiating the reactions. Ethanol was found to have a stronger adsorption on gold compared to silver and copper, as determined by binding energy calculations. The nature of bonding was studied using natural bond orbital (NBO) analysis and quantum theory of atoms-in-molecules (QTAIM). The reactive intermediates, activated complexes, transition states, and bond breaking on different metal cluster catalysts were calculated along with cycle kinetics. High resolution mass spectroscopy was used to observe the coupling products, which confirmed the kinetic- and thermodynamic-allowed reaction pathway of Guerbet coupling of ethanol. The highest selectivity for butanol (61%) was achieved after 2 hours of reaction time, while the highest ethanol conversion (91%) was achieved after 5 hours of reaction time.
JOURNAL OF CLUSTER SCIENCE
(2023)
Article
Engineering, Chemical
Karthikeyan K. Ramasamy, Michel Gray, Heather Job, Yong Wang
CHEMICAL ENGINEERING SCIENCE
(2015)
Article
Chemistry, Applied
Mariefel V. Olarte, Alan H. Zacher, Asanga B. Padmaperuma, Sarah D. Burton, Heather M. Job, Teresa L. Lemmon, Marie S. Swita, Leslie J. Rotness, Gary N. Neuenschwander, John G. Frye, Douglas C. Elliott
TOPICS IN CATALYSIS
(2016)
Article
Chemistry, Applied
Karthikeyan K. Ramasamy, Michel Gray, Heather Job, Daniel Santosa, Xiaohong Shari Li, Arun Devaraj, Abhi Karkamkar, Yong Wang
TOPICS IN CATALYSIS
(2016)
Article
Chemistry, Applied
Michael A. Lilga, Asanga B. Padmaperuma, Deanna L. Auberry, Heather M. Job, Marie S. Swita
Article
Materials Science, Coatings & Films
Vijayakumar Murugesan, Michel Gray, Mond Guo, Heather Job, Libor Kovarik, Arun Devaraj, Suntharampillai Thevuthasan, Karthikeyan K. Ramasamy
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2019)
Article
Chemistry, Physical
Balakrishna Maddi, Stephen Davidson, Heather Job, Robert Dagle, Mond Guo, Michel Gray, Karthikeyan K. Ramasamy
Summary: A Co-based catalyst was developed for the direct conversion of fossil and biomass derived syngas into light olefins with high conversion and selectivity. Optimized Co loading and HZSM-5 acidity levels were crucial to achieving high levels of C-2-C-5 olefin selectivity.
Article
Chemistry, Multidisciplinary
Hongliang Wang, Hao Ruan, Maoqi Feng, Yuling Qin, Heather Job, Langli Luo, Chongmin Wang, Mark H. Engelhard, Erik Kuhn, Xiaowen Chen, Melvin P. Tucker, Bin Yang
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.