Article
Chemistry, Organic
Fengyi Li, Yating Liang, Xuan Zhan, Sheng Zhang, Man-Bo Li
Summary: An electrochemical redox-neutral C(sp(3))-H amidation was developed using N-alkoxyamide as an amidating reagent. N-alkoxyamides exhibited higher reactivity compared to direct reactions with primary amides. This novel approach allowed for the synthesis of a wide range of bioactive amides and direct derivatization of pharmaceuticals under oxidant- and transition metal-free conditions. Solar energy could be directly utilized in this electrochemical transformation, providing a clean and practical method for amide synthesis.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Jean-Marc I. A. Lawrence, Paul E. Floreancig
Summary: This work presents a method for electrochemical oxoammonium ion regeneration by understanding the relationship between intermediate cation stability and reaction kinetics, which can expand the scope of electrocatalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Minju Chung, Kyoungsuk Jin, Joy S. Zeng, Thu N. Ton, Karthish Manthiram
Summary: Selective and efficient electrocatalysts are crucial for the successful deployment of electrochemistry for synthetic applications. In this study, iridium-decorated manganese oxide nanoparticles were synthesized through galvanic replacement reactions, demonstrating high partial current density and Faradaic efficiency. Operando X-ray absorption spectroscopy results revealed that the leaching of manganese ions from the nanoparticles during the galvanic replacement process resulted in structural changes and increased presence of electrophilic oxygen atoms on the catalyst surface, enhancing the electrocatalytic activity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Wan Ru Leow, Simon Voelker, Raoul Meys, Jianan Erick Huang, Shaffiq A. Jaffer, Andre Bardow, Edward H. Sargent
Summary: The production of hydrogen and hydrocarbon refining contribute significantly to CO2 emissions in the chemicals industry. Coupled electrification can cut emissions by up to 39%, even with the current electricity mix. Chemicals manufacturing is a major greenhouse gas emitter, with over half of the emissions coming from ammonia and oxygenates. By using electrolyzer systems that convert hydrocarbons to oxygenates and generate H-2 from water, emissions from fossil-based ammonia and oxygenates can be reduced by up to 88%. Low-carbon electricity is not necessary for a substantial reduction in global chemical industry emissions, as a 39% reduction can be achieved with the electricity carbon footprint available in the US or China today. Researchers interested in this area are provided with considerations and recommendations.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Aaron G. Nash, Colton J. Breyer, Brett D. Vincenzini, Gregory I. Elliott, Jens Niklas, Oleg G. Poluektov, Arnold L. Rheingold, Diane K. Smith, Djamaladdin G. Musaev, Douglas B. Grotjahn
Summary: This study reports a catalyst that maintains high electrocatalytic turnover frequency at very low pH values, with high current densities and excellent durability. Preliminary computational studies suggest that the sulfonate group in the active site acts as a proton relay even in strong acid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Haiying Wei, Tongtong Wei, Licheng Li, Tingwei Zhang, Farzad Seidi, Yongcan Jin, Huining Xiao
Summary: Three types of Pt/CeO2 catalysts (rod-shaped (CeO2-R), cube-shaped (CeO2-C), and octahedral-shaped (CeO2-O)) with different support morphologies were synthesized and investigated for catalytic oxidation of C2H4 at low temperatures. The catalysts showed shape-dependent catalytic activity, with Pt/CeO2-O exhibiting the highest activity. This can be attributed to the different oxygen species activated by the catalysts in the C2H4 oxidation process. Additionally, the negative impact of water condensation on the catalyst can be eliminated by refreshing the catalyst with N2 purging. Overall, this work provides a novel catalytic system for efficient low-temperature ethylene oxidation and enhances our understanding of the catalytic mechanism.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Review
Chemistry, Multidisciplinary
Wan-Chi Hsu, Yu-Heng Wang
Summary: This Review summarizes the current status of molecular water oxidation catalysts (MWOCs) based on transition metals, focusing on their kinetic and thermodynamic properties, and discusses the effects of ligand classes on the catalyst performance.
Article
Chemistry, Physical
Jiaojiao Song, Yixuan Yang, Shoujie Liu, Lei Li, Nan Yu, Yuteng Fan, Zhiming Chen, Long Kuai, Baoyou Geng
Summary: This study investigates the impact of dispersion and support on the activity of Pt in CO oxidation reaction, revealing that reducible TiO2 significantly influences Pt activity with lower apparent activation barriers, and that single-atom dispersion of Pt maximizes active sites.
Article
Multidisciplinary Sciences
Yuting Zhou, Joaquin Rodriguez-Lopez, Jeffrey S. Moore
Summary: Post-consumer plastic waste has prompted the development of deconstruction methods to recover valuable substances, but depolymerization of highly crystalline engineering thermoplastics remains challenging. In this study, the authors demonstrate the electrochemical depolymerization of polyoxymethylene into repolymerizable monomer under ambient conditions. Through various experiments, they uncover the heterogeneous electro-mediated acid depolymerization mechanism and the dual role of the co-solvent HFIP. This research highlights the potential of electromediated depolymerization in sustainable chemistry by merging renewable energy and circular plastic economy concepts.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Bjarne Kreitz, Patrick Lott, Jongyoon Bae, Katrin Blondal, Sofia Angeli, Zachary W. Ulissi, Felix Studt, C. Franklin Goldsmith, Olaf Deutschmann
Summary: This study utilizes the Reaction Mechanism Generator (RMG) to automatically generate microkinetic models for the oxidation of combustion byproducts from stoichiometric gasoline direct injection engines on Pt catalysts. By combining first-principles mechanism construction and top-down parameter refinement, the study is able to describe experimental results and provide guidance for other challenging catalytic reactions.
Article
Chemistry, Physical
Bjarne Kreitz, Patrick Lott, Jongyoon Bae, Katrin Blondal, Sofia Angeli, Zachary W. Ulissi, Felix Studt, C. Franklin Goldsmith, Olaf Deutschmann
Summary: This study tackles the challenge of identifying reaction networks in complex exhaust gas mixtures by using the Reaction Mechanism Generator (RMG) to automatically generate microkinetic models. The combination of first-principles-based mechanism construction and top-down parameter refinement allows for a comprehensive description of experimental results. This research serves as a blueprint for utilizing RMG in other challenging heterogeneous catalyzed reactions.
Article
Chemistry, Physical
Shi He, Yufeng Chen, Mengdi Wang, Hanggai Nuomin, Peter Novello, Xueqian Li, Siyuan Zhu, Jie Liu
Summary: Ammonia is a promising hydrogen mediator that reduces the cost of hydrogen transportation, but improvements are needed for extracting hydrogen. Ammonia electrolysis is a convenient method for low-cost hydrogen production. Nickel-cobalt nitride nanosheets show high electrocatalytic activity for the ammonia oxidation reaction in non-aqueous solutions.
Article
Chemistry, Analytical
Xin Chang, Christopher Batchelor-McAuley, Richard G. Compton
Summary: The study investigates the methanol oxidation reaction at the single nanoparticle scale under aqueous alkaline conditions. It is found that the catalytic activity of single nanoparticles can be preserved in ensembles of nanoparticles, reaching maximum catalytic rate at a potential of +0.05 V.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Wan-Chi Hsu, Wan-Qin Zeng, I-Chung Lu, Tzuhsiung Yang, Yu-Heng Wang
Summary: This study synthesized dinuclear cobalt complexes with bis(benzimidazole)pyrazolide-type ligands and evaluated their performance as molecular electrocatalysts for water oxidation. The results showed that the complex with a non-innocent ligand exhibited faster catalytic turnover than the other complex under alkaline conditions, suggesting a different mechanism. This study highlights the use of non-innocent ligands as a valuable strategy for designing effective metal-based molecular water oxidation catalysts.
Article
Chemistry, Physical
Aleksandra Selivanova, Victoria G. Demina, Egor E. Aydakov, Andrey A. Saraev, Vasily V. Kaichev, Valerii Bukhtiyarov
Summary: The oxidation of methanol on a Pt(1 1 1) single crystal surface was found to start at around 350 K, producing mainly CO2 and methyl formate. Key intermediates in the reaction include CO and formaldehyde, with formates exhibiting low thermal stability and carbonates showing extremely high thermal stability. Carbonates, along with CO, can inhibit the oxidation of methanol on the platinum surface.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Applied
A. Serve, A. Boreave, B. Cartoixa, K. Pajot, P. Vernoux
Summary: This study investigates the catalytic activity of Ag nanoparticles dispersed on various supports with different redox properties for soot combustion. The results show that the catalytic performance is related to the Ag surface concentration, and different contact modes have different impacts on catalytic performances. Moreover, the catalysts show remarkable hydrothermal stability after ageing.
Article
Environmental Sciences
Salah Eddine Sbai, Chunlin Li, Antoinette Boreave, Nicolas Charbonnel, Sebastien Perrier, Philippe Vernoux, Farida Bentayeb, Christian George, Sonia Gil
Summary: Through an atmospheric experiment conducted in Lyon, it was found that urban air has a high potential to form secondary organic aerosol (SOA), primarily influenced by OH radical photochemical oxidation rather than ozonolysis. The correlation between SOA formation and ambient environment conditions was also observed during the study.
JOURNAL OF ENVIRONMENTAL SCIENCES
(2021)
Article
Chemistry, Physical
K. Beliaeva, N. Grimaldos-Osorio, E. Ruiz-Lopez, L. Burel, P. Vernoux, A. Caravaca
Summary: The production of H-2 via electrolysis is considered the best alternative to traditional catalytic reforming processes. Research aims to gain deeper insights into the cleavage of main chemical bonds in the complex lignin structure across different Ni oxidation states.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Engineering, Chemical
Florian Maurer, Andreas Gaenzler, Patrick Lott, Benjamin Betz, Martin Votsmeier, Stephane Loridant, Philippe Vernoux, Vadim Murzin, Benjamin Bornmann, Ronald Frahm, Olaf Deutschmann, Maria Casapu, Jan-Dierk Grunwaldt
Summary: The study found that reductive pulse activation leads to an increase in overall catalyst activity and the generation of different particle size zones within the catalyst bed. Activation temperature and pulse length influence the noble metal particle size, and this activation method could potentially be applied to industrially relevant catalysts in the future.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2021)
Article
Chemistry, Physical
Jie Yu, Angel Caravaca, Chantal Guillard, Philippe Vernoux, Liang Zhou, Lingzhi Wang, Juying Lei, Jinlong Zhang, Yongdi Liu
Summary: A highly efficient photocatalyst for degrading toluene has been developed, capable of converting 93% of toluene into non-toxic products. This enhanced performance is attributed to the inverse opal structure and the incorporation of carbon nitride quantum dots.
Article
Chemistry, Multidisciplinary
Fatiha Hamidi, Hanane Chaker, Sonia Gil, Leila Cherif, Karima Saidi, Philippe Vernoux
Summary: This study successfully synthesized an ordered nanostructured mesoporous titanosilicate through a new synthesis path and supported silver nanoparticles on it. Experimental results confirmed that the support of silver nanoparticles can significantly enhance the catalytic activity of mesoporous titanosilicate, especially in the oxidation of carbon monoxide.
RESEARCH ON CHEMICAL INTERMEDIATES
(2021)
Article
Chemistry, Physical
Jie Yu, Frederic Dappozze, Juan Martin-Gomez, Jesus Hidalgo-Carrillo, Alberto Marinas, Philippe Vernoux, Angel Caravaca, Chantal Guillard
Summary: The valorization of glycerol into high added-value products by photocatalysis not only creates good economic benefits, but also meets global low-carbon and energy-saving environmental protection needs. This study found that WO3-based materials exhibit outstanding selectivity towards valuable oxidation products like glyceraldehyde, establishing a new starting point for the development of advanced materials for efficient glycerol valorization.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Electrochemistry
B. Gilbert, T. Cavoue, M. Aouine, L. Burel, F. J. Cadete Santos Aires, A. Caravaca, M. Rieu, J. P. Viricelle, S. Bruyere, D. Horwat, S. Migot, P. Vilasi, P. Vernoux
Summary: The study investigates the possibility of electrochemically producing active oxygen species on Ag-based ceramic electrodes in a solid oxide electrochemical cell. It was found that small Ag clusters formed in Ag/YSZ cermet layers were selective for epoxidation, but the sintering process happened too quickly to maintain EO selectivity. On the other hand, Ag/GDC cermet coatings demonstrated a linear increase in selectivity towards EO and ethylene conversion with applied current, indicating the direct electrooxidation of ethylene into EO.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Physical
Jeffrey T. Miller, Neil M. Schweitzer, Mimoun Aouine, Philippe Vernoux, Abdelmalik Boufar, Juliette Blanchard, Jean-Marc Krafft, Christophe Methivier, Celine Sayag, Frederic Ser, Mickael Sicard, Cyril Thomas
Summary: Supported transition metal materials are deemed as ideal catalysts for reactions in hydrocarbon refining, energy, and environmental catalysis. This study shows that deposition of oxotungstates coupled with selective deposition of Rh on CeO2 surface can significantly reduce Rh sintering after reduction, potentially due to decreased nucleation sites and physical barrier effects. The findings suggest that Rh sub-nanometric clusters must be thin and small for efficient catalytic activity.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Environmental Sciences
A. Molino, M. Hamandi, R. Grosjean, F. Dappozze, L. Lamaa, L. Peruchon, C. Brochier, K. Dembele, M. El Hajem, P. Vernoux, C. Guilard, H. Kaper
Summary: This study investigates the interaction between a photocatalyst (TiO2) and a catalyst (Pt/TiO2 and Pt/CeO2) in the oxidation of formaldehyde and toluene at room temperature. The presence of the catalyst and photocatalyst enhances the catalytic performance for formaldehyde oxidation but decreases the photocatalytic performance for toluene oxidation. The overall performance of the system can be optimized by selecting the support material for the catalyst, controlling the amount of Pt used, and adjusting the ratio of catalyst to photocatalyst. Different configurations of the photocatalyst and catalyst on the textile are also studied, with the gas stream passing through the textile being the most effective.
Article
Chemistry, Physical
N. Grimaldos-Osorio, F. Sordello, M. Passananti, J. Gonzalez-Cobos, A. Bonhomme, P. Vernoux, A. Caravaca
Summary: Developing sustainable processes for plastic recycling is an important environmental issue. Electro-oxidation of plastic waste in electrolyzers powered by renewable energies is a promising option to produce hydrogen at lower temperatures with reduced energy demand. However, the dissolution strategy of PMMA still has some drawbacks that degrade the electrochemical performance of the electrode.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Physical
Simon Fahed, Remy Pointecouteau, Mimoun Aouine, Antoinette Boreave, Sonia Gil, Valerie Meille, Philippe Bazin, Olivier Toulemonde, Alain Demourgues, Marco Daturi, Philippe Vernoux
Summary: This study describes the properties and catalytic activity of Pr-rich cerium-zirconium-praseodymium (CZP) oxides for propane and CO oxidation. The concentration of oxygen vacancies can be controlled by adjusting the quantity of Pr3+ cations. A high-energy grinding step can increase the Pr3+ concentration and enhance the reducibility and catalytic activity. Pr-rich CZP oxides show better performance in diesel oxidation catalyst applications.
APPLIED CATALYSIS A-GENERAL
(2022)
Article
Chemistry, Physical
Jie Yu, Jesus Gonzalez-Cobos, Frederic Dappozze, Francisco J. Lopez-Tenllado, Jesus Hidalgo-Carrillo, Alberto Marinas, Philippe Vernoux, Angel Caravaca, Chantal Guillard
Summary: Photoelectrocatalytic glycerol oxidation is a promising technology for simultaneous biomass waste utilization and hydrogen production. By applying an external bias, the photo-catalytic activity and stability of monoclinic WO3 catalyst have been enhanced for the selective generation of value-added products under near-neutral conditions.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Physical
Simon Fahed, Remy Pointecouteau, Mimoun Aouine, Antoinette Boreave, Sonia Gil, Philippe Bazin, Alain Demourgues, Marco Daturi, Philippe Vernoux
Summary: Improving the activity of emission control catalysts in urban mode at low temperatures can be achieved by tailoring the metal-support interaction between platinum group metals (PGMs) and ceria. In this study, dispersing a small amount of Pd on Pr-rich cerium-zirconium-praseodymium mixed oxides led to efficient CO oxidation at low temperatures, but required a pre-reduction step to promote propane oxidation. However, the fast re-oxidation and re-dispersion of Pd nanoparticles by the high oxygen mobility of the mixed oxide rapidly deactivated the catalysts in lean conditions.
Review
Chemistry, Physical
Jesus Gonzalez-Cobos, Mathieu S. Prevot, Philippe Vernoux
Summary: Lignin electrolysis offers the possibility of co-generating valuable aromatic compounds and green H2 with lower energy cost than traditional water electrolysis. This review provides an overview of anode materials and cells investigated in different conditions and summarizes the remaining challenges. Low-temperature electrolyzers can be integrated in biorefineries for lignin conversion and hydrogen co-generation.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
