Owing to the increasing emissions of carbon dioxide (CO2), human life and the ecological environment have been affected by global warming and climate changes. To mitigate the concentration of CO2 in the atmosphere various strategies have been implemented such as separation, storage, and utilization of CO2. Although it has been explored for many years, hydrogenation reaction, an important representative among chemical conversions of CO2, offers challenging opportunities for sustainable development in energy and the environment. Indeed, the hydrogenation of CO2 not only reduces the increasing CO2 buildup but also produces fuels and chemicals. In this critical review we discuss recent developments in this area, with emphases on catalytic reactivity, reactor innovation, and reaction mechanism. We also provide an overview regarding the challenges and opportunities for future research in the field (319 references).

Recent advances in catalytic hydrogenation of carbon dioxide

The interfaces of Cu/ZnO and Cu/ZrO2 play vital roles in the hydrogenation of CO2 to methanol by these composite catalysts. Surface structural reorganization and particle growth during catalysis deleteriously reduce these active interfaces, diminishing both catalytic activities and MeOH selectivities. Here we report the use of preassembled bpy and Zr6(μ3-O)4(μ3-OH)4 sites in UiO-bpy metal–organic frameworks (MOFs) to anchor ultrasmall Cu/ZnOx nanoparticles, thus preventing the agglomeration of Cu NPs and phase separation between Cu and ZnOx in MOF-cavity-confined Cu/ZnOx nanoparticles. The resultant Cu/ZnOx@MOF catalysts show very high activity with a space–time yield of up to 2.59 gMeOH kgCu–1 h–1, 100% selectivity for CO2 hydrogenation to methanol, and high stability over 100 h. These new types of strong metal–support interactions between metallic nanoparticles and organic chelates/metal-oxo clusters offer new opportunities in fine-tuning catalytic activities and selectivities of metal nanoparticles@MOFs.

Confinement of Ultrasmall Cu/ZnOx Nanoparticles in Metal–Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2

This Communication describes the hydrogenation of carbon dioxide to methanol via tandem catalysis with dimethylamine and a homogeneous ruthenium complex. Unlike previous examples with homogeneous catalysts, this CO2-to-CH3OH process proceeds under basic reaction conditions. The dimethylamine is proposed to play a dual role in this system. It reacts directly with CO2 to produce dimethylammonium dimethylcarbamate, and it also intercepts the intermediate formic acid to generate dimethylformamide. With the appropriate selection of catalyst and reaction conditions, >95% conversion of CO2 was achieved to form a mixture of CH3OH and dimethylformamide.

Tandem amine and ruthenium-catalyzed hydrogenation of CO2 to methanol.

Pd/ZnO catalysts for direct CO2 hydrogenation to methanol

All commercial catalysts for methanol synthesis and for the water–gas shift reaction in the low temperature region contain zinc oxide in addition to the main active component, copper. The varied benefits of zinc oxide are analysed here. The formation of zincian malachite and other copper/zinc hydroxy carbonates is essential in the production of small, stable copper crystallites in the final catalyst. Further, the regular distribution of copper crystallites on the zinc oxide phase ensures long catalyst life. Zinc oxide also increases catalyst life in the water–gas shift process by absorbing sulphur poisons but it is not effective against chloride poisons. In methanol synthesis, zinc oxide (as a base) removes acidic sites on the alumina phase which would otherwise convert methanol to dimethyl ether. Although bulk reduction of zinc oxide to metallic zinc does not take place, reduction to copper–zinc alloy (brass) can occur, sometimes as a surface phase only. A new interpretation of conflicting measurements of adsorbed oxygen on the copper surfaces of methanol synthesis catalysts is based on the formation of Cu–O–Zn sites, in addition to oxygen adsorbed on copper alone. The possible role of zinc oxide as well as copper in the mechanisms of methanol synthesis is still the subject of controversy. It is proposed that, only under conditions of deficiency of adsorbed hydrogen on the copper phase, hydrogen dissociation on zinc oxide, followed by hydrogen spillover to copper, is significant.

The role of zinc oxide in Cu/ZnO catalysts for methanol synthesis and the water–gas shift reaction

Cu–Zn hydroxycarbonates have been studied as precursors of Cu–ZnO catalysts, with particular reference to the effect on catalyst activity of ageing the precursor prior to decomposition and reduction. The precursor obtained by precipitation from mixed nitrate solution (Cu/Zn molar ratio 2:1) at 333 K and pH 7.0 consisted of zincian malachite (Cu/Zn ≈ 85:15) and aurichalcite. The precursor was aged in the mother liquor at 333 K for various times. Characterisation by XRD, i.r., DTA, electron microscopy, EDAX and XPS showed that ageing led to loss of the aurichalcite and production of a more finely divided copper-enriched (Cu/Zn = 2:1) malachite phase. The unaged precursor yielded a catalyst of low activity for both methanol synthesis (studied at 50 bar and at 1 bar) and the reverse water-gas shift reaction. The aged precursor gave catalysts of much higher activity for both reactions. Increased ageing did not change the selectivity ratio for methanol synthesis vs. reverse shift in the CO2+ H2 reaction at normal pressure.

Copper–zinc oxide catalysts. Activity in relation to precursor structure and morphology

Comparison is made between Cu–ZnO and alumina-supported Cu–ZnO as catalysts for the reverse water-gas shift (RWGS) reaction For both types of catalyst the Cu/Zn ratio has been varied between Cu-rich and Zn-rich compositions By applying X-ray diffractometry, X-ray line broadening, optical reflectance spectroscopy and other techniques the effects on the structural and physical properties of the hydroxycarbonate precursors, the calcined products and the ultimately derived catalysts are determined The presence of alumina decreases the crystallite size of the CuO and ZnO particles produced on calcination and at high Cu/Zn ratios increases the dispersion of copper in the final catalyst The activities of the catalysts for the RWGS reaction at 513K are compared and the most active are shown to be those which are Cu rich (Cu/Zn > 3) and contain alumina as support The activities of all the catalysts can be rationalized by referring the activity to unit surface area of copper metal

Cu–ZnO and Cu–ZnO/Al2O3 Catalysts for the Reverse Water-Gas Shift Reaction. The Effect of the Cu/Zn Ratio on Precursor Characteristics and on the Activity of the Derived Catalysts

David Waller

Papers

Copper–zinc oxide catalysts. Activity in relation to precursor structure and morphology

Cu–ZnO and Cu–ZnO/Al2O3 Catalysts for the Reverse Water-Gas Shift Reaction. The Effect of the Cu/Zn Ratio on Precursor Characteristics and on the Activity of the Derived Catalysts

Copper-zinc oxide catalysts