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TiO2-supported Pd NPs-based materials were prepared following two distinct approaches: For the first set of materials 1–8, modification of the TiO2 support was performed prior to Pd NPs deposition, while the second set (9–15) was synthesized by deposition of modifiers over pre-synthesized Pd-PPh3/TiO2. These catalysts were applied in the hydrogenation of CO2 to formate, and their performance was compared with that of the unmodified Pd-PPh3/TiO2. Modification of the TiO2 support by organosilanes provided a beneficial effect in catalysis compared with the catalyst containing unmodified TiO2 or TiO2 modified by organophosphonic acids. In contrast, in most cases, the deposition of modifiers over previously synthesized Pd NPs supported on TiO2 was not beneficial to the activity of the catalyst. Interestingly, upon recycling, the first set of catalysts suffered a rapid decrease in activity, while the anchoring of modifiers over previously formed Pd NPs showed an improved stability (TON > 500 after the third recycling). [ABSTRACT FROM AUTHOR]

Catalytic conversion of CO2 to CO via the reverse water gas shift (RWGS) reaction has been identified as a promising approach for CO2 utilization and mitigation of CO2 emissions. Bare Pt shows low activity for the RWGS reaction due to its low oxophilicity, with few research works having concentrated on the inverse metal oxide/Pt catalyst for the RWGS reaction. In this work, MnOx was deposited on the Pt surface over a SiO2 support to prepare the MnOx/Pt inverse catalyst via a co-impregnation method. Addition of 0.5 wt% Mn to 1 wt% Pt/SiO2 improved the intrinsic reaction rate and turnover frequency at 400 °C by two and twelve times, respectively. Characterizations indicate that MnOx partially encapsulates the surface of the Pt particles and the coverage increases with increasing Mn content, which resembles the concept of strong metal–support interaction (SMSI). Although the surface accessible Pt sites are reduced, new MnOx/Pt interfacial perimeter sites are created, which provide both hydrogenation and C-O activation functionalities synergistically due to the close proximity between Pt and MnOx at the interface, and therefore improve the activity. Moreover, the stability is also significantly improved due to the coverage of Pt by MnOx. This work demonstrates a simple method to tune the oxide/metal interfacial sites of inverse Pt-based catalyst for the RWGS reaction. [ABSTRACT FROM AUTHOR]

H2 has aroused significant attention as an unpolluted and renewable energy carrier. However, the efficient storage and controllable release of H2 are urgent to be addressed. Through the hydrogenation of CO2 (bicarbonate) to produce formic acid (formate) and reverse dehydrogenation reactions, a carbon-neutral formic acid-based hydrogen cycle system can be established. Given the excellent recyclability and facile separation of heterogeneous catalysis, the development of heterogeneous catalysts for these reversible interconversions is thoroughly summarized, with a special focus on the structure–activity relationship and the mechanistic insight. Finally, the challenges and opportunities surrounding the formic acid-based hydrogen cycle system are discussed. It is hoped that this review will provide guidance and an idea for the design and development of efficient heterogeneous catalysts for the carbon-neutral H2 storage and release system. [ABSTRACT FROM AUTHOR]

Catalytic gas-phase hydrogenation of CO2 into CH4 was tested under three different nickel/aluminate catalysts obtained from precursors of hexaaluminate composition (MAl16O19, M = Mg, Ca, Ba). These catalysts were prepared using a carbon template method, where carbon is self-generated from a sol-gel that contains an excess of citric acid and the Al and M salts (Ba2+, Ca2+, Mg2+) by two-step calcination in an inert/oxidizing atmosphere. This procedure yielded Ni particles decorating the surface of a porous high surface area matrix, which presents a typical XRD pattern of aluminate structure. Ni particles are obtained with a homogeneous distribution over the surface and an average diameter of ca 25–30 nm. Obtained materials exhibit a high conversion of CO2 below 500 °C, yielding CH4 as a final product with selectivity >95%. The observed trend with the alkaline earth cation follows the order NiBaAlO-PRx > NiCaAlO-PRx > NiMgAlO-PRx. We propose that the high performance of the NiBaAlO sample is derived from both an appropriate distribution of Ni particle size and the presence of BaCO3, acting as a CO2 buffer in the process. [ABSTRACT FROM AUTHOR]

Catalytic carbon dioxide (CO2) hydrogenation to carbon monoxide (CO) via reverse water-gas shift (RWGS) reaction is of particular interest due to its direct use in various industrial processes as feedstock. However, the competitive CO2 methanation process severely limits the RWGS reaction in a lower temperature range. In this context, we propose a novel nanocatalyst (NC) comprising oxygen vacancy-enriched subnanometer-scale CoPd hybrid cluster (CoOxVPd)-anchored Pd nanoparticles (NPs) on cobalt oxide support underneath (denoted as CP-CoOxVPd) by using a galvanic replacement reaction-assisted wet chemical reduction method. As-developed CP-CoOxVPd NC initiated the RWGS reaction at 423 K temperature while showing an optimum CO production yield of ∼3414 μmol g−1catalyst and a CO selectivity as high as ∼99% at 523 K in the reaction gas of CO2:H2 = 1:3. The results of physical characterizations along with electrochemical and gas chromatography (GC) suggest that abundant oxygen vacancies in the surface-anchored CoOxVPd clusters are vital for CO2 adsorption and subsequent activation, while neighboring Pd domains facilitate the H2 dissociation. The obtained results are expected to provide a feasible design of Co-based NCs for the RWGS reaction. [ABSTRACT FROM AUTHOR]

The catalytic conversion of CO2 to CO by the reverse water gas shift (RWGS) reaction followed by well-established synthesis gas conversion technologies could be a practical technique to convert CO2 to valuable chemicals and fuels in industrial settings. For catalyst developers, prevention of side reactions like methanation, low-temperature activity, and selectivity enhancements for the RWGS reaction are crucial concerns. Cerium oxide (ceria, CeO2) has received considerable attention in recent years due to its exceptional physical and chemical properties. This study reviews the use of ceria-supported active metal catalysts in RWGS reaction along with discussing some basic and fundamental features of ceria. The RWGS reaction mechanism, reaction kinetics on supported catalysts, as well as the importance of oxygen vacancies are also explored. Besides, recent advances in CeO2 supported metal catalyst design strategies for increasing CO2 conversion activity and selectivity towards CO are systematically identified, summarized, and assessed to understand the impacts of physicochemical parameters on catalytic performance such as morphologies, nanosize effects, compositions, promotional abilities, metal-support interactions (MSI) and the role of selected synthesis procedures for forming distinct structural morphologies. This brief review may help with future RWGS catalyst design and optimization. [ABSTRACT FROM AUTHOR]

Integrated CO2 capture and hydrogenation to produce formate offers a sustainable approach for reducing carbon dioxide emissions and producing liquid hydrogen carriers (formate) simultaneously. In the current study, three different types of aqueous amine solutions including monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) were investigated as CO2-capturing and hydrogenation agents in the presence of a Pd/NAC catalyst. The effect of amine structures on the CO2 absorption products and formate yield was investigated thoroughly. It was found that the formate product was successfully produced in the presence of all three aqueous amine solutions, with tertiary amine TEA accounting for the highest formate yield under the same CO2 loadings. This is due to the fact that primary and secondary amine moieties in MEA and DEA are responsible for the formation of CO2 adducts of carbamate and bicarbonate, whereas the tertiary amine moiety in TEA is responsible for the formation of hydrogenation-favorable bicarbonate as the solo CO2 absorption product. A high yield of formate of 82.6% was achieved when hydrogenating 3 M TEA with 0.3 mol CO2/mol amine solution in the presence of a Pd/NAC catalyst. In addition, the physio-chemical properties of the Pd/NAC catalyst analyzed using TEM, XRD and XPS characterization were applied to rationalize the superior catalytic performance of the catalyst. The reaction mechanism of integrated CO2 capture and hydrogenation to produce formate in aqueous amine solutions over Pd/NAC catalyst was proposed as well. [ABSTRACT FROM AUTHOR]

Metallic Pt sites are imperative in the CO oxidation reaction. Herein, we demonstrate the tuning of Pt sites by treating a Pt catalyst in various reductive atmospheres, influencing the catalyst activities in low-temperature CO oxidation. The H2 pretreatment of Pt clusters at 200 °C decreases the T50 from 208 °C to 183 °C in the 0.1 wt % Pt/TiO2 catalyst. The T50 shows a remarkable improvement using a CO pretreatment, which decreases the T50 further to 135 °C. A comprehensive characterization study reveals the integrated reasons behind this phenomenon: (i) the extent of PtO transition to metallic Pt sites, (ii) the ample surface active oxygen triggered by metallic Pt, (iii) the CO selectively adsorbs on metallic Pt sites which participate in low-temperature CO oxidation, and (iv) the formation of the unstable intermediate such as bicarbonate, contributes together to the enhanced activity of CO pretreated Pt/TiO2. [ABSTRACT FROM AUTHOR]

Copper catalysts were widely developed for CO2 conversion, but suffered severe sintering at temperatures higher than 300 °C. Platinum was the most active and stable metal for RWGS reactions. However, the high price and scarcity of platinum restrained its application. Downsizing the metal particles can significantly improve the atom efficiency of the precious metal but the size effect of Pt on RWGS reactions was still unclear. In the present work, the single atomic Pt on SrTiO3 was prepared using an impregnation leaching method, and the catalyst showed significant activity for an RWGS reaction, achieving a CO2 conversion rate of 45%, a CO selectivity of 100% and a TOF of 0.643 s−1 at 500 °C. The structures of the catalysts were characterized using XRD, STEM and EXAFS. Especially, the size effect of Pt in RWGS was researched using in situ FTIR and DFT calculations. The results reveal that single Pt atoms are the most active species in RWGS via a "–COOH route" while larger Pt cluster and nanoparticles facilitate the further hydrogenation of CO. The reaction between formate and H* is the rate determination step of an RWGS reaction on a catalyst, in which the reaction barrier can be lowered from 1.54 eV on Pt clusters to 1.29 eV on a single atomic Pt. [ABSTRACT FROM AUTHOR]

A series of Ni-xSi/ZrO2 (x = 0, 0.1, 0.5, 1 wt%, the controlled contents of Si) catalysts with a controlled nickel content of 10 wt% were prepared by the co-impregnation method with ZrO2 as support and Si as a promoter. The effect of different amounts of Si on the catalytic performance was investigated for CO2 methanation with the stoichiometric H2/CO2 molar ratio (4/1). The catalysts were characterized by BET, XRF, H2-TPR, H2-TPD, H2-chemisorption, CO2-TPD, XRD, TEM, XPS, and TG-DSC. It was found that adding the appropriate amount of Si could improve the catalytic performance of Ni/ZrO2 catalyst at a low reaction temperature (250 °C). Among all the catalysts studied, the Ni-0.1Si/ZrO2 catalyst showed the highest catalytic activity, with H2 and CO2 conversion of 73.4% and 72.5%, respectively and the yield of CH4 was 72.2%. Meanwhile, the catalyst showed high stability and no deactivation within a 10 h test. Adding the appropriate amount of Si could enhance the interaction between Ni and ZrO2, and increase the Ni dispersion, the amounts of active sites including surface Ni0, oxygen vacancies, and strong basic sites on the catalyst surface. These might be the reasons for the high activity and selectivity of the Ni-0.1Si/ZrO2 catalyst. [ABSTRACT FROM AUTHOR]

CO2 hydrogenation toward methane, a reaction of high environmental and sustainable energy importance, was investigated at 200–600 °C and H2/CO2 = 4/1, over Rh nanoparticles dispersed on supports with different oxygen storage capacity characteristics (γ-Al2O3, alumina-ceria-zirconia, and ceria-zirconia). The effects of the support OSC and Rh particle size on reaction behavior under both integral and differential conditions were investigated, to elucidate the combined role of these crucial catalyst design parameters on methanation efficiency. A volcano-type variation of methanation turnover frequency was found in respect to support OSC; Rh/ACZ, with intermediate OSC, was the optimal catalyst. The structure sensitivity of the reaction was found to be a combined function of support OSC and Rh particle size: For Rh/γ-Al2O3 (lack of OSC) methanation was strongly favored on small particles—the opposite for Rh/CZ (high OSC). The findings are promising for rational design and optimization of CO2 methanation catalysts by tailoring the aforementioned characteristics. [ABSTRACT FROM AUTHOR]

High surface area cobalt-lanthanide bimetallic aerogels were successfully synthesized by the epoxide addition method. The bimetallic aerogels were calcined at two different temperatures and either bimetallic oxides containing oxychlorides, Co3O4.3LnOCl (Ln = La, Sm, Gd, Dy and Yb) or perovskites, LnCoO3 (Ln = La, Sm, Gd and Dy) were obtained at 500 or 900 °C, respectively. The exceptions are the aerogels of cerium and ytterbium, which after oxidation at 500 and 900 °C, stabilize as sesquioxides: Co3O4.3CeO2 and 2Co3O4.3Yb2O3, the first at both temperatures and the second only at the highest temperature. The bimetallic cobalt-lanthanide oxychlorides or perovskites were tested as catalysts for the methanation of CO2. The cobalt catalytic activity is determined by the type and acid-base properties of the lanthanide oxide phase and by its pre-reduction under hydrogen. The best results were those obtained over the calcined aerogels pre-reduced under hydrogen. In particular, the highest values were those obtained over the Co-Ce aerogel calcined at 900 °C that in the same conditions present an activity comparable to that measured over a 5 wt.% Rh catalyst supported on alumina, one of the literature references. The activity and the selectivity increase with the catalysts' basicity, showing an inverse dependence of the reduction temperature that decreases along the lanthanide series either for the aerogels calcined at 500 or 900 °C. In general, the basicity of the aerogels calcined at 900 °C (perovskites) is higher and they are more active but less selective than those calcined at 500 °C (oxychlorides), which to our knowledge is for the first time reported for the methanation of CO2. [ABSTRACT FROM AUTHOR]

Mesoporous Ni-based catalysts with Ni confined in nanochannels are widely used in CO2 methanation. However, when Ni loadings are high, the nanochannels are easily blocked by nickel particles, which reduces the catalytic performance. In this work, three-dimensional mesoporous Ni-CeO2-CSC catalysts with high Ni loadings (20−80 wt %) were prepared using a colloidal solution combustion method, and characterized by nitrogen adsorption–desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and H2 temperature programmed reduction (H2-TPR). Among the catalysts with different Ni loadings, the 50% Ni-CeO2-CSC with 50 wt % Ni loading exhibited the best catalytic performance in CO2 methanation. Furthermore, the 50% Ni-CeO2-CSC catalyst was stable for 50 h at 300° and 350 °C in CO2 methanation. The characterization results illustrate that the 50% Ni-CeO2-CSC catalyst has Ni particles smaller than 5 nm embedded in the pore walls, and the Ni particles interact with CeO2. On the contrary, the 50% Ni-CeO2-CP catalyst, prepared using the traditional coprecipitation method, is less active and selective for CO2 methanation due to the larger size of the Ni and CeO2 particles. The special three-dimensional mesoporous embedded structure in the 50% Ni-CeO2-CSC can provide more metal–oxide interface and stabilize small Ni particles in pore walls, which makes the catalyst more active and stable in CO2 methanation. [ABSTRACT FROM AUTHOR]

Ni-Ce-Zr-Oδ catalysts were prepared via one-pot hydrothermal synthesis. It was found that Ni can be partially incorporated into the Ce-Zr lattice, increasing surface oxygen species. The catalysts possess high surface areas even at high Ni loadings. The catalyst with Ni content of 71.5 wt.% is able to activate CO2 methanation even at a low temperature (200 °C). Its CO2 conversion and methane selectivity were reported at 80% and 100%, respectively. The catalyst was stable for 48 h during the course of CO2 methanation at 300 °C. Catalysts with the addition of medium basic sites were found to have better catalytic activity for CO2 methanation. [ABSTRACT FROM AUTHOR]

The resistance to sintering of Ni/Al2O3 catalysts with different additives for methanation reaction was modeled and predicted by data mining. In the screening, the resistance to sintering of Na, Ca, Ce, Mg, La, Cu, Zn, Zr, In, Mo, and Ti promoted Ni/Al2O3 catalyst were measured in terms of the increased rate of the size of the metallic nickel particles. The resistance to sintering of catalysts, described by the increased rate of Ni particle size as well as basic physicochemical properties of the 11 selected elements, was adopted for optimization model construction by data mining. Through regression model prediction and experimental verification, Cs was found to be an additive, and promotes the resistance to sintering mostly for Ni/Al2O3 catalysts. This result provides further evidence that data mining techniques can be employed as a highly efficient tool for the discovery of new catalysts in comparison with the traditional experimental method. [ABSTRACT FROM AUTHOR]

In this work, we present an investigation concerning the evaluation of the catalytic properties of Ni nanoparticles supported on ZrO2, SiO2, and MgAl2O4 for CO2 hydrogenation to methane. The supports were prepared by coprecipitation and sol-gel, while Ni was incorporated by impregnation (10–20 wt %). X-ray diffraction, nitrogen physisorption, temperature-programmed reduction, H2 pulse chemisorption, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy were the main characterization techniques employed. A laboratory fixed-bed reactor operated at atmospheric pressure, a temperature range of 350–500 °C, and a stoichiometric H2/CO2 molar ratio was used for catalyst evaluation. The most outstanding results were obtained with nickel catalysts supported on ZrO2 with CO2 conversions of close to 60%, and selectivity to methane formation was 100% on a dry basis, with high stability after 250 h of reaction time. The majority presence of tetragonal zirconia, as well as the strong Ni–ZrO2 interaction, were responsible for the high catalytic performance of the Ni/ZrO2 catalysts. [ABSTRACT FROM AUTHOR]

The conversion of CO2 into CO via the Reverse Water–Gas Shift (RWGS) reaction is a suitable route for CO2 valorisation. Fe-based catalysts are highly active for this reaction, but their activity and selectivity can be substantially boosted by adding Cs as a promoter. In this work we demonstrate that Cs modifies the redox behaviour and the surface chemistry of the iron-based materials. The metallic dispersion and the amount of metallic Fe centres available for the reaction depends on Cs loading. 5 wt. % of Cs is an optimum amount of dopant to achieve a fair activity/selective balance. Nevertheless, depending on the RWGS reactor operational temperature, lower concentrations of Cs also lead to acceptable catalytic performance. Along with the excellent activity of the prepared materials this work showcases their robustness for long-term runs and the strong impact of H2/CO ratio in the overall catalytic performance. [ABSTRACT FROM AUTHOR]