The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.

Methanol synthesis via CO2 hydrogenation is a key step in methanol-based economy. This reaction is catalyzed by supported copper nanoparticles and displays strong support or promoter effects. Zirconia is known to enhance both the methanol production rate and the selectivity. Nevertheless, the origin of this observation and the reaction mechanisms associated with the conversion of CO2 to methanol still remain unknown. Here, we present a mechanistic study of the hydrogenation of CO2 on Cu/ZrO2. Using kinetics, in situ IR and NMR spectroscopies and isotopic labeling strategies, we examined the surface intermediates during CO2 hydrogenation at different pressures. Combined with DFT calculations, we show that formate species is the reaction intermediate and that the zirconia/copper interface is a key for its conversion to methanol.The catalytic hydrogenation of carbon dioxide to methanol is a key process in the sustainable methanol-based economy. [1] While copper-based catalysts are highly active for this transformation, [2] their activity and selectivity strongly depend on the support and/or the promoters. Understanding the copper-support interaction -its effect on the activity and product selectivity -has been a very intensive field of research over the last decade. While the reaction mechanisms and the nature of the active sites on Cu/ZnO systems have been extensively investigated, [3] copper supported on zirconia and related materials also exhibits high activity and selectivity in CO2 hydrogenation to methanol (Eq. 1) by minimizing the formation of CO, a byproduct often resulting from the competitive reverse water-gas shift reaction (Eq. 2). [4] CO2 + 3H2 = CH3OH + H2O ∆rH° (500 K) = -62 kJ.mol -1 (1) CO2 + H2 = CO + H2O ∆rH° (500 K) = +40 kJ.mol -1 (2)Although the copper-zirconia interface was proposed to play a key role in the selective formation of methanol, [4c, 4e-g] the active site and the reaction mechanism, including the role of the interface on methanol selectivity, are still not understood. In fact, mechanistic investigations using Diffuse Reflectance IR Fourier Transform spectroscopy (DRIFTS) led to opposite conclusions: formate is an intermediate in methanol formation [4c, 4d] vs. CO2 is first reduced to CO that is in turn hydrogenated to methanol through a carboxyl intermediate. [4f] Herein, by using a combined experimental and computational approach on realistic models, we investigated the reaction mechanism of CO2 hydrogenation to methanol on a Cu/ZrO2 catalyst. Kinetic investigation, in situ and ex situ spectroscopies -FTIR and NMRtogether with isotopic labeling and computational modelling showed that methanol is a primary product formed by the hydrogenation of formate as a reaction intermediate. First, narrowly dispersed copper nanoparticles supported on monoclinic zirconia were prepared by a molecular approach. [5] Grafting of [Cu(O t Bu)]4 on the surface hydroxyl groups of the support ( Figure S1-S2, Scheme S1) followed by a treatment under H2 at 500 °C for 5 h [6] yields smal...

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Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. Here we report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2°C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. The formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelastic neutron scattering experiments and synchrotron X-ray powder diffraction. These findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).

Management of carbon on Earth has become one of the central themes in science, society,a nd politics owing to continuous relocation of carbon from the underground to the atmosphere in the form of carbon dioxide (CO 2 ). This is ac onsequenceo ft he modern life of mankind largely relying on burning or utilising carbon-based fossil fuels, which also causes their depletion. Recently,g lobalw arminga nd consequent climate change have been ascribed to the increasingc oncentration of atmosphericg reen-houseg ases,m ostr epresented by CO 2 ,a nd the world is joining forces to reduce the amount of CO 2 emissiont ot he atmosphere and convertt he "waste" CO 2 into valuable chemicals like polymers and fuels.CO 2 is at hermodynamically stable molecule with the standard formation enthalpy of À393.5 kJ mol À1 . [1] However,C O 2 can be transformed with notable reactivity depending on the chemicale nvironment. Among them catalysis offerss pecific sites to activateC O 2 for its chemical transformation. While CO 2 to polymers is generally enabled by efficient homogeneous catalysts (i.e. reactants and catalyst are in the same liquid phase), large-scale production of useful chemicals like fuels necessitates continuous operation using heterogeneous catalyst to activate CO 2 over its surface. There are several activation methods overc atalyst surfacer eported to date and each methodg enerally leads characteristicr eactivityo fC O 2 and products due to the unique form of activated CO 2 during transformation. Thisa rticle aims at concisely describing the reactivity of CO 2 in general, summarising the state-of-the-art activation methods and also highlighting similarities in different modes of CO 2 activation and correlations to product selectivity to evaluatec oherent views on CO 2 transformation over catalytic surfaces.The general properties of the CO 2 molecule, associatedw ith its reactivity,are summarised in the following four points: 1) Bending of CO 2For the uncharged state, bending of the molecule from its linear equilibrium geometry induces changes in the shape and energy level of the molecular orbitals. Notably,t he more bent the geometry,t he lower the energy level of the in-plane (i.e. to the plane of bending) contribution of 2p u orbital( the lowest unoccupied molecular orbital, LUMO) as shown in Figure 1. Changing the OCO bond angle from 1808 to 1578,t he proportion of the LUMO on the carbon is increased from 61 %t o 78 %, while the distance between carbon ando xygen (< 0.01 )a nd the energy (DE < 0.5 eV) remaina lmostc onstant. [2] Importantly,t his loweringo ft he in-plane 2p u orbital (LUMO) energy upon bending makest he carbon atom electrophilic. 2) Repartition of the ChargesWhen isolated, ap ositive chargec an be found on the carbon atom (the Mulliken's population is + 0.368 e) and negative chargeso nt he two oxygen atoms (with ap opulation of À0.184 e). [3] Ap olarized mediuml ike water can increase the charge on the carbon to + 0.407 e( obtained by DFT using a polarizable continuumm odel with al inear geometry). [3]...

The reaction mechanism of reverse water-gas shift (RWGS) reaction was investigated using two commercial gold-based catalysts supported on Al2O3 and TiO2. The surface species formed during the reaction and reaction mechanisms were elucidated by transient and steady-state operando DRIFTS studies. It was revealed that RWGS reaction over Au/Al2O3 proceeds through the formation of formate intermediates that are reduced to CO. In the case of Au/TiO2 catalyst, the reaction goes through a redox mechanism with the suggested formation of hydroxycarbonyl intermediates, which further decompose to CO and water. The Ti 3+ species, the surface hydroxyls, 2 and oxygen vacancies jointly participate. The absence of carbonyl species adsorbed on gold particles during the reaction for both catalysts indicates that the reaction pathway involving dissociative adsorption of CO2 on Au particles can be discarded. To complete the study Operando UV-Vis spectroscopy was successfully applied to confirm the presence of Ti 3+ and to understand the role of the oxygen vacancies of TiO2 support in activating CO2 and thus the subsequent RWGS reaction.

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In dye sensitized solar cells, three structurally similar dyes are commonly employed to sensitize anatase nano-crystals, namely the cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II) dye (N3), its twice deprotonated (N719) and completely deprotonated (N712) form. Using density functional theory, several possible binding geometries of these dyes are identified on the anatase(101) surface. Computed relative energies show that protonation of the surface can strongly influence the relative stabilities of these configurations, and could induce a conformational transition from double bidentate-bridged binding to mixed bidentate/monodentate binding. Attenuated total reflection (ATR)-IR experiments and computed vibrational spectra provide additional support for a protonation dependent equilibrium between two different configurations. Furthermore, self-assembly in chains of hydrogen bonded dye molecules seems structurally favorable on the anatase(101) surface, for enantiopure dyes a packing density of 0.744/nm 2 could be achieved.