The utilization of fossil fuels has enabled an unprecedented era of prosperity and advancement of well-being for human society. However, the associated increase in anthropogenic carbon dioxide (CO2) emissions can negatively affect global temperatures and ocean acidity. Moreover, fossil fuels are a limited resource and their depletion will ultimately force one to seek alternative carbon sources to maintain a sustainable economy. Converting CO2 into value-added chemicals and fuels, using renewable energy, is one of the promising approaches in this regard. Major advances in energy-efficient CO2 conversion can potentially alleviate CO2 emissions, reduce the dependence on nonrenewable resources, and minimize the environmental impacts from the portions of fossil fuels displaced. Methanol (CH3OH) is an important chemical feedstock and can be used as a fuel for internal combustion engines and fuel cells, as well as a platform molecule for the production of chemicals and fuels. As one of the promising approaches, thermocatalytic CO2 hydrogenation to CH3OH via heterogeneous catalysis has attracted great attention in the past decades. Major progress has been made in the development of various catalysts including metals, metal oxides, and intermetallic compounds. In addition, efforts are also put forth to define catalyst structures in nanoscale by taking advantage of nanostructured materials, which enables the tuning of the catalyst composition and modulation of surface structures and potentially endows more promising catalytic performance in comparison to the bulk materials prepared by traditional methods. Despite these achievements, significant challenges still exist in developing robust catalysts with good catalytic performance and long-term stability. In this review, we will provide a comprehensive overview of the recent advances in this area, especially focusing on structure-activity relationship, as well as the importance of combining catalytic measurements, in situ characterization, and theoretical studies in understanding reaction mechanisms and identifying key descriptors for designing improved catalysts.

Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis.

CO2 electroreduction reaction (CO2RR) to fuels and feedstocks is an attractive route to close the anthropogenic carbon cycle and store renewable energy. The generation of more reduced chemicals, especially multicarbon oxygenate and hydrocarbon products (C2+) with higher energy density is highly desirable for industrial applications. However, selective conversion of CO2 to C2+ suffers from high overpotential, low reaction rate and low selectivity, and the process is extremely sensitive to the catalyst structure and electrolyte. Here we discuss strategies to achieve high C2+ selectivity through rational design of the catalyst and electrolyte. Current state-of-the-art catalysts, including Cu and Cu-bimetallic catalysts as well as alternative materials are considered. The importance of taking into consideration the dynamic evolution of the catalyst structure and composition are highlighted, focusing on findings extracted from in situ and operando characterizations. Additional theoretical insight into the reaction mechanisms underlying the improved C2+ selectivity of specific catalyst geometries/compositions in synergy with a well-chosen electrolyte are also provided.

Rational Catalyst and Electrolyte Design for Co2 Electroreduction Towards Multicarbon Products

Monoclinic zirconia has been uncovered as a carrier able to substantially boost the activity of indium oxide for CO2 hydrogenation to methanol. Here, electronic, geometric, and interfacial phenomen...

Role of Zirconia in Indium Oxide-Catalyzed CO2 Hydrogenation to Methanol

Utilization of CO2 as feedstock to produce fine chemicals and renewable fuels is a highly promising field, which presents unique challenges in its implementation at scale. Heterogeneous catalysis w...

Advances in the Design of Heterogeneous Catalysts and Thermocatalytic Processes for CO2 Utilization

Carbon dioxide (CO2) hydrogenation to methanol with H2 produced with renewable energy represents a promising path for the effective utilization of a major anthropogenic greenhouse gas, in which cat...

CO2Hydrogenation to Methanol over In2O3-Based Catalysts: From Mechanism to Catalyst Development

We present a comprehensive mechanistic study on the highly tunable selectivity over Inx/ZrO2 catalysts in CO2 hydrogenation. By variation of the indium loading between 0.1 and 5 wt %, either an adm...

Unraveling Highly Tunable Selectivity in CO 2 Hydrogenation over Bimetallic In-Zr Oxide Catalysts

It is challenging to elucidate the mechanism of CO2 methanation reaction over nickel-based catalysts and precisely tune the kinetics of rate-determining-step. In this work, we propose a strategy to engineer the oxygen vacancies of nickel-based catalysts for enhanced CO2 methanation. A Y2O3-promoted NiO-CeO2 catalyst is prepared and found to exhibit an outstanding methanation activity that is up to three folds higher than NiO-CeO2 and six folds higher than NiO-Y2O3 at mild reaction temperatures (

Vacancy engineering of the nickel-based catalysts for enhanced CO2 methanation

Formation and influence of surface hydroxyls on product selectivity during CO2 hydrogenation by Ni/SiO2 catalysts

The present invention relates to a supported nickel-based catalyst for a carbon dioxide methanation reaction, wherein the supported nickel-based catalyst is a mixed oxide comprising the following components by weight: 3 parts of nickel oxide, 4-6 parts of a metal oxide carrier, and 1-3 parts of a doped metal oxide. Compared with the catalyst in the prior art, the catalyst of the present inventionhas the following characteristics that the doped modified carrier is used, the methane yield is greatly improved compared with the single carrier on the basis of the maintaining of high selectivity, especially the increase at a low temperature section (250 DEG C) exceeds 100%, and the highest increase is 78%. According to the present invention, the stability of the catalyst of the present invention is higher than the stability of the catalyst supported by cerium oxide so as to overcome the bottleneck in the integration of activity, selectivity and stability of the existing catalytic system; and the catalyst can be prepared by a co-precipitation method, and the method has characteristics of simpleness and adjustable cerium/yttrium ratio, and is suitable for large-scale industrial production.

Xinyu Cao

Papers

Unraveling Highly Tunable Selectivity in CO 2 Hydrogenation over Bimetallic In-Zr Oxide Catalysts

Vacancy engineering of the nickel-based catalysts for enhanced CO2 methanation

Formation and influence of surface hydroxyls on product selectivity during CO2 hydrogenation by Ni/SiO2 catalysts

Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof