A computational study of direct CO₂ hydrogenation to methanol on Pd surfaces

Abstract

The reaction mechanism of direct CO2 hydrogenation to methanol is investigated in detail on Pd (111), (100) and (110) surfaces using density functional theory (DFT), supporting investigations into emergent Pd-based...

Dynamic Evolution of Methane Oxidation on Pd-Based Catalysts: A Reactive Force Field Molecular Dynamics Study

“…It should be pointed out that the paths of CH 2 O + OH → H 2 COOH and CH 2 O + O → H 2 COO were ignored in the previous DFT studies of methane oxidation ,,− and first observed in our present work. In previous studies, H 2 COO and H 2 COOH have been reported during the hydrogenation of CO 2 to methanol . Such two steps can be observed due to the high activity of lattice oxygen and the smaller barriers of 0.20 and 0.57 eV compared with the dehydrogenation of CH 2 O to CHO with the barrier of 1.15 eV, which might provide alternative mechanisms at a molecular level to form the complete oxidation product CO 2 .…”

“…To understand the details of the formation process of the complete oxidation product CO 2 over PdO (101), here the trajectory of every CH 4 molecule that participates in the reactions is analyzed and summarized in Scheme 1. As Scheme 45 Such two steps can be observed due to the high activity of lattice oxygen and the smaller barriers of 0.20 and 0.57 eV compared with the dehydrogenation of CH 2 O to CHO with the barrier of 1.15 eV, which might provide alternative mechanisms at a molecular level to form the complete oxidation product CO 2 . Our simulations show that 11 methane molecules dissociate and no CO 2 is formed on the Pd (111) surface with oxygen coverage of 3/9 ML, while 21 methane molecules dissociate and CO 2 is observed on the PdO (101) surface, indicating that PdO may be more active than Pd for methane oxidation.…”

Density functional theoretical study of the tungsten-doped In2O3 catalyst for CO2 hydrogenation to methanol

“…CO 2 utilization has attracted much attention with the rapid development of sustainable hydrogen. 1–5 Among the various utilization options, CO 2 hydrogenation to methanol (CO 2 + 3H 2 ⇋ CH 3 OH + H 2 O, = −49.3 kJ mol −1 ; = +3.5 kJ mol −1 ) is a preferable candidate since methanol is an important chemical intermediate and liquid fuel. 1 A methanol economy was even proposed for CO 2 utilization by Prof. George Andrew Olah, 6 based on CO 2 hydrogenation to methanol.…”

“…CO 2 utilization has attracted much attention with the rapid development of sustainable hydrogen. [1][2][3][4][5] Among the various utilization options, CO 2 hydrogenation to methanol (CO 2 + 3H 2 ! CH 3 OH + H 2 O, DH 298K = À49.3 kJ mol À1 ; DH 298K = +3.5 kJ mol À1 ) is a preferable candidate since methanol is an important chemical intermediate and liquid fuel.…”

Extensively amino-functionalized graphene captures carbon dioxide

“…The different means of CO 2 chemical fixation, separation, and conversion to improve its storage are being currently developed. 27,[35][36][37][38][39][40][41][42][43] The synthesis of valuable reactants out of abundant CO 2 instead of its geological storage represents a perspective and seemingly quite successful direction of research in synthetic chemistry. The latter greatly benefits from the explosive development of novel fascinating catalysis schemes.…”