The chemical transformation of CO2 not only mitigates the anthropogenic CO2 emission into the Earth’s atmosphere but also produces carbon compounds that can be used as precursors for the production of chemicals and fuels. The activation and conversion of CO2 can be achieved on multifunctional catalytic sites available at the metal/oxide interface by taking advantage of the synergy between the metal nanoparticles and oxide support. Herein, we look at the recent progress in mechanistic studies of CO2 hydrogenation to C1 (CO, CH3OH, and CH4) compounds on metal/oxide catalysts. On this basis, we are able to provide a better understanding of the complex reaction network, grasp the capability of manipulating structure and combination of metal and oxide at the interface in tuning selectivity, and identify the key descriptors to control the activity and, in particular, the selectivity of catalysts. Finally, we also discuss challenges and future research opportunities for tuning the selective conversion of CO2 on ...

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Tuning Selectivity of CO2 Hydrogenation Reactions at the Metal/Oxide Interface

CO2 hydrogenation to hydrocarbons is a promising way of making waste to wealth and energy storage, which also solves the environmental and energy issues caused by CO2 emissions Much efforts and research are aimed at the conversion of CO2 via hydrogenation to various value-added hydrocarbons, such as CH4, lower olefins, gasoline, or long-chain hydrocarbons catalyzed by different catalysts with various mechanisms This review provides an overview of advances in CO2 hydrogenation to hydrocarbons that have been achieved recently in terms of catalyst design, catalytic performance and reaction mechanism from both experiments and density functional theory calculations In addition, the factors influencing the performance of catalysts and the first C–C coupling mechanism through different routes are also revealed The fundamental factor for product selectivity is the surface H/C ratio adjusted by active metals, supports and promoters Furthermore, the technical and application challenges of CO2 conversion into useful fuels/chemicals are also summarized To meet these challenges, future research directions are proposed in this review

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A short review of recent advances in CO2 hydrogenation to hydrocarbons over heterogeneous catalysts

A zirconia supported nickel catalyst for CO2 methanation has been prepared via a rapid and effective plasma decomposition of nickel precursor at atmospheric pressure and temperature around 150 °C, followed by hydrogen reduction at 500 °C. The obtained Ni/ZrO2 catalyst shows high Ni dispersion with principally exposed Ni(111) lattice plane. An enhanced cooperation between Ni and interfacial active sites is achieved as well, which leads to rapid dissociative adsorption of H2 and hydrogen spillover. Sufficient H atoms are thereby generated for CO2 hydrogenation and helpful to create oxygen vacancies on the ZrO2 surface. Higher basicity correlated to the oxygen vacancies further enhances CO2 adsorption and activation. Hence, a superior low temperature activity for CO2 methanation was achieved. For example, a CO2 conversion of 71.9% with a CH4 yield of 69.5% was achieved over the plasma decomposed catalyst at 300 °C with a feeding gas consisting of H2 (32 ml min−1), CO2 (8 ml min−1) and N2 (10 ml min−1) at a GHSV of 60,000 h-1. The corresponding TOF value towards CO2 conversion is 0.61 s-1. However, the CO2 conversion, CH4 yield and TOF value are only 32.9%, 30.3% and 0.39 s-1 at the same reaction conditions over the thermally prepared catalyst. The operando DRIFT analyses demonstrate that CO2 methanation over the plasma decomposed catalyst follows the CO-hydrogenation route. The exposed high-coordinate Ni(111) facets of the plasma decomposed catalyst facilitate the decomposition of CO2 and formates into adsorbed CO. The subsequent hydrogenation of adsorbed CO leads to the production of methane. However, the thermally decomposed catalyst with complex Ni crystal structure and more defects mainly takes the pathway of direct formate hydrogenation. The present study confirms the structure of Ni/ZrO2 has significant effect on the catalytic activity for CO2 methanation.

Structural effect of Ni/ZrO2 catalyst on CO2 methanation with enhanced activity

A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales.

Y. C. Chang

Papers

Methanation of CO2 and reverse water gas shift reactions on Ni/SiO2 catalysts: the influence of particle size on selectivity and reaction pathway