CO₂ Hydrogenation on Cu/Al₂O₃: Role of the Metal/Support Interface in Driving Activity and Selectivity of a Bifunctional Catalyst

Abstract

Selective hydrogenation of CO 2 into methanol is ak ey sustainable technology,w here Cu/Al 2 O 3 prepared by surface organometallic chemistry displays high activity to-wardsC O 2 hydrogenation compared to Cu/SiO 2 ,y ielding CH 3 OH, dimethyl ether (DME), and CO.C H 3 OH formation rate increases due to the metal-oxide interface and involves formate intermediates according to advanced spectroscopyand DFT calculations.A l 2 O 3 promotes the subsequent conversion of CH 3 OH to DME, showing bifunctional catalysis,b ut also increases the rate of CO formation. The latter takes place 1) directly by activation of CO 2 at the metal-oxide interface, and 2) indirectly by the conversion of formate surface species and CH 3 OH to methyl formate,w hich is further decomposed into CH 3 OH and CO.T his study shows howA l 2 O 3 ,aLewis acidic and non-reducible support, can promote CO 2 hydrogenation by enabling multiple competitive reaction pathways on the oxide and metal-oxide interface.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Mechanistic and multiscale aspects of thermo-catalytic CO2conversion to C1products

“…280,281 Other materials investigated for CO 2 hydrogenation to methanol are Au/CeO x / TiO 2 , 282 In 2 O 3 , [283][284][285][286][287] Ir-In 2 O 3 , 288 Ni-In 2 O 3 , 289 Mn-Co, 290 Ni-Ga, 291 ZnO-ZrO 2 , 292 GaPd 2 , 293 and Co/SiO 2 . 91 In particular, In 2 O 3 is attracting great interest in the scientific community [283][284][285][286][287] because of its high catalyst stability 265,286 and very high methanol selectivity. [294][295][296][297][298] However, there is still a debate on the currently available best catalyst of methanol synthesis from CO 2 , mainly because the performances of the catalysts strongly depend on the experimental conditions under which they are tested.…”

“…[261][262][263] The production of H 2 O enhances also the sintering of the catalyst. [70][71][72][73][74]263 To overcome these challenges, different support materials, which can promote structural and electronic properties and stabilize smaller Cu particles, 264 were investigated, including ZrO 2 , 265,266 La 2 O 3 , 267 MoC 2 , 267 CeO 2 , 268 and La 2 O 2 CO 3 (ref. 267) and ZnO-ZrO 2 .…”

CO2 hydrogenation over heterogeneous catalysts at atmospheric pressure: from electronic properties to product selectivity

“…In addition, the specific interfacial sites between the active metal and the support also modify the catalyst selectivity. [131][132][133]…”

Dynamics and Site Isolation: Keys to High Propane Dehydrogenation Performance of Silica-Supported PtGa Nanoparticles

“…While there are several reports regarding the interaction of clusters with surface, 84 − 92 modeling the interaction between nanoparticles (at least one nanometer large) and a surface, especially if the latter is an amorphous surface such as silica is a real modeling challenge. Born–Oppenheimer (BO) Ab Initio Molecular Dynamic (AIMD) with annealing at high temperatures ( vide infra ) was used to explore the conformational space of Pt and PtGa nanoparticles (37 atoms, 1 nm diameter) on silica surfaces, starting from the vacuum optimized nanoparticles deposited on silica or Ga-doped silica surface.…”