Dataset Information

CO₂ Hydrogenation to Methanol over Cd₄/TiO₂ Catalyst: Insight into Multifunctional Interface.

ABSTRACT: Supported metal catalysts have shown to be efficient for CO₂ conversion due to their multifunctionality and high stability. Herein, we have combined density functional theory calculations with microkinetic modeling to investigate the catalytic reaction mechanisms of CO₂ hydrogenation to CH₃OH over a recently reported catalyst of Cd₄/TiO₂. Calculations reveal that the metal-oxide interface is the active center for CO₂ hydrogenation and methanol formation via the formate pathway dominates over the reverse water-gas shift (RWGS) pathway. Microkinetic modeling demonstrated that formate species on the surface of Cd₄/TiO₂ is the relevant intermediate for the production of CH₃OH, and CH₂O^# formation is the rate-determining step. These findings demonstrate the crucial role of the Cd-TiO₂ interface for controlling the CO₂ reduction reactivity and CH₃OH selectivity.

SUBMITTER: Li G

PROVIDER: S-EPMC9305886 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Publications

CO2 Hydrogenation to Methanol over Cd4/TiO2 Catalyst: Insight into Multifunctional Interface.

Li Guanna G Meeprasert Jittima J Wang Jijie J Li Can C Pidko Evgeny A EA

ChemCatChem 20220127 5

Supported metal catalysts have shown to be efficient for CO2 conversion due to their multifunctionality and high stability. Herein, we have combined density functional theory calculations with microkinetic modeling to investigate the catalytic reaction mechanisms of CO2 hydrogenation to CH3OH over a recently reported catalyst of Cd4/TiO2. Calculations reveal that the metal-oxide interface is the active center for CO2 hydrogenation ...[more]

PMID: 35909897

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Project description:Methanol synthesized from carbonate hydrogenation is of great importance for CO2 utilization indirectly. Herein, a series of Cu/Zn/Al heterogeneous catalysts were prepared by co-precipitation with a synchronous aging step, and were applied for hydrogenation of diethyl carbonate (DEC) to produce methanol. Furthermore, the catalysts were characterized by physicochemical methods, such as N2 adsorption, ICP-OES, N2O titration, SEM, TEM, XRD, H2-TPR and XPS in detail. Higher copper concentration led to a higher ratio of bulk CuOx species in the calcined samples, which resulted in different copper species distribution after the reduction process. Structure activity relationship analysis indicated that the balance of surface Cu0 and Cu+ species influenced the formation rate of methanol. A higher proportion of Cu+ to (Cu+ + Cu0) was conductive to methanol formation, while excessive Cu0 site density played a negative influence on the methanol synthesized from DEC. Cu/Zn/Al with a 45.2% weight fraction of copper showed better performance with a total methanol formation rate of 131.0 mg gcat. -1 h-1. The reaction temperature and reaction time could obviously affect the reaction performance and the results suggested that 200 °C and 6 h were suitable. Furthermore, the long-term stability and activity of the catalyst was also studied on a fixed bed, and the yield of total methanol reached to 88.5% and the selectivity of total methanol gradually decreased to 74.0% within 200 h, which could be attributed to the detrimental influence derived from the increase of Cu0. The reaction pathways involved in the hydrogenation of DEC process were proposed. The substance scope was also extended to other carbonates and the catalyst exhibited superior catalytic performance toward linear carbonates. This work provided insights into carbonate hydrogenation over an effective Cu/Zn/Al catalyst, which could be utilized into upgrading CO2 indirectly to produce commodity methanol under relatively mild reaction conditions.

Project description:Low temperature and high pressure are thermodynamically more favorable conditions to achieve high conversion and high methanol selectivity in CO2 hydrogenation. However, low-temperature activity is generally very poor due to the sluggish kinetics, and thus, designing highly selective catalysts active below 200 °C is a great challenge in CO2-to-methanol conversion. Recently, Re/TiO2 has been reported as a promising catalyst. We show that Re/TiO2 is indeed more active in continuous and high-pressure (56 and 331 bar) operations at 125-200 °C compared to an industrial Cu/ZnO/Al2O3 catalyst, which suffers from the formation of methyl formate and its decomposition to carbon monoxide. At lower temperatures, precise understanding and control over the active surface intermediates are crucial to boosting conversion kinetics. This work aims at elucidating the nature of active sites and active species by means of in situ/operando X-ray absorption spectroscopy, Raman spectroscopy, ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Transient operando DRIFTS studies uncover the activation of CO2 to form active formate intermediates leading to methanol formation and also active rhenium carbonyl intermediates leading to methane over cationic Re single atoms characterized by rhenium tricarbonyl complexes. The transient techniques enable us to differentiate the active species from the spectator one on TiO2 support, such as less reactive formate originating from spillover and methoxy from methanol adsorption. The AP-XPS supports the fact that metallic Re species act as H2 activators, leading to H-spillover and importantly to hydrogenation of the active formate intermediate present over cationic Re species. The origin of the unique reactivity of Re/TiO2 was suggested as the coexistence of cationic highly dispersed Re including single atoms, driving the formation of monodentate formate, and metallic Re clusters in the vicinity, activating the hydrogenation of the formate to methanol.

Dataset Information

CO₂ Hydrogenation to Methanol over Cd₄/TiO₂ Catalyst: Insight into Multifunctional Interface.

Publications

CO<sub>2</sub> Hydrogenation to Methanol over Cd<sub>4</sub>/TiO<sub>2</sub> Catalyst: Insight into Multifunctional Interface.

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