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Methyl formate was produced in one pot through the hydrogenation of CO to formic acid/formate followed by an esterification step. The route offers the possibility to integrate renewable energy into the fossil-based chemical value chain. In this work, a phosphine-polymer-anchored Ru complex was shown to be an efficient solid catalyst for the direct hydrogenation of CO to methyl formate. The 1,2-bis(diphenylphosphino)ethane-like polymer presented the highest activity with a turnover number (TON) of up to 3401 at 160 °C. The reaction parameters were systemically investigated to optimize the reaction towards the formation of methyl formate. This catalyst could be reused seven times without a significant decrease in activity. Evolution of the catalytic Ru center during the reaction was revealed, and a possible reaction mechanism was proposed.
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http://dx.doi.org/10.1002/cssc.201900808 | DOI Listing |
ACS Earth Space Chem
August 2025
Centre de Recherche sur les Ions, les Matériaux et la Photonique Normandie University, ENSICAEN, UNICAEN, CEA, CNRS, CIMAP, Caen 14000, France.
Studying the physicochemical properties of ice in astronomical environments is crucial to understanding the chemical processes involved in cosmic events such as comet and planet formation. The physical characteristics and chemical evolution on the surfaces of cosmic objects such as comets or interstellar grains offer key insights into these processes. This study focuses on α-pinene, a carbon- and hydrogen-rich molecule, which serves as a model for investigating radical-driven synthesis of more complex molecules under space-like conditions.
View Article and Find Full Text PDFAdv Mater
July 2025
Department of Chemistry, University of Bayreuth, Universitatsstraße 30, 95447, Bayreuth, Germany.
Green hydrogen is critical to establish a sustainable energy future as it offers a clean, renewable, and a versatile alternative for decarbonizing industries, transportation, and power generation. However, the limitations of current methods significantly restrict the scope and hinder many of the envisioned applications. This study aims to report on the first example of a 3d-metal-based (Cu) heterogeneous photocatalytic system to produce green hydrogen via dehydrogenation of methyl formate (MF), a reaction previously known to require 4d/5d transition metals.
View Article and Find Full Text PDFChemSusChem
July 2025
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, 208016, India.
Readily accessible enones are the building blocks for synthesizing three different classes of compounds, viz, functionalized ketones, allylic alcohols, and saturated alcohols through selective hydrogenation. However, accessing all three congeners under a single chemodivergent protocol remains challenging due to the inherent reactivity difference between CC and CO bonds. In general, the lower-energy 1,4-addition of a metal hydride preferentially reduces the CC bond over the CO bond.
View Article and Find Full Text PDFInorg Chem
June 2025
Department of Chemistry, Indian Institute of Technology (BHU), Varanasi, UP 221005, India.
Formic acid has a high hydrogen storage capacity and is a valuable chemical for industrially important reactions. The industrial production of formic acid proceeds through the carbonylation of methanol to form methyl formate and its subsequent hydrolysis. This process requires high temperature and pressure, and it relies on the use of fossil fuels.
View Article and Find Full Text PDFPhys Chem Chem Phys
May 2025
Key Laboratory of Advanced Technologies of Materials, Ministry of Education, Southwest Jiaotong University, Chengdu 610031, China.
Amino radicals play a central role in the pyrolysis and oxidation of ammonia. The practical utilization of pure ammonia as a fuel still faces several challenges. The dual-fuel combustion strategy, which involves blending low-reactivity NH with high-reactivity fuels, can effectively address these issues.
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