Metal-support Interaction Effect Research Articles

Single-atom Pt-I3 sites on all-inorganic Cs2SnI6 perovskite for efficient photocatalytic hydrogen production

Organic-inorganic lead halide perovskites are a new class of semiconductor materials with great potential in photocatalytic hydrogen production, however, their development is greatly plagued by their low photocatalytic activity, instability of organic component and lead toxicity in particular. Herein, we report an anti-dissolution environmentally friendly Cs2SnI6 perovskite anchored with a new class of atomically dispersed Pt-I3 species (PtSA/Cs2SnI6) for achieving the highly efficient photocatalytic hydrogen production in HI aqueous solution at room temperature. Particularly, we discover that Cs2SnI6 in PtSA/Cs2SnI6 has a greatly enhanced tolerance towards HI aqueous solution, which is very important for achieving excellent photocatalytic stability in perovskite-based HI splitting system. Remarkably, the PtSA/Cs2SnI6 catalyst shows a superb photocatalytic activity for hydrogen production with a record turnover frequency of 70.6 h−1per Pt, about 176.5 times greater than that of Pt nanoparticles supported Cs2SnI6 perovskite, along with superior cycling durability. Charge-carrier dynamics studies in combination with theory calculations reveal that the dramatically boosted photocatalytic performance on PtSA/Cs2SnI6 originates from both unique coordination structure and electronic property of Pt-I3 sites, and strong metal-support interaction effect that can not only greatly promote the charge separation and transfer, but also substantially reduce the energy barrier for hydrogen production. This work opens a new way for stimulating more research on perovskite composite materials for efficient hydrogen production.

Palladium nanoparticles anchored on Schiff base metal complex derived heteroatom-doped carbon materials for boosting ethanol electrooxidation

Designing appropriate support for noble metal-based catalyst has consistently been an effective strategy to improve the catalytic activity of ethanol electrooxidation reaction (EOR). Here, a novel heteroatom-doped carbon (HDC) material has been prepared by calcination of Schiff base metal complex precursor. The HDC-750 prepared at the optimum temperature (750 °C) has a three-dimensional structure with large specific surface area and unique pores. When the HDC-750 is used as a support for palladium nanoparticles, it can improve the conductivity of catalysts, the permeability of electrolyte and intermediates, and increase the number of anchoring points of palladium nanoparticles. Due to its unique three-dimensional structure and the synergistic enhancement effect of strong metal support interaction between Pd and HDC-750, the Pd/HDC-750 catalyst exhibits high electrochemical active surface area (23.94 m2 gPd−1) and excellent EOR activity (146.3 mA cm−2), which is as high as 2.1 and 3.0 times of that for the Pd/C. After 3600 s durability test, the Pd/HDC-750 shows a high current density of 9.9 mA cm−2, while Pd/C shows only 1.3 mA cm−2.

Boron Nanosheet-Supported Rh Catalysts for Hydrogen Evolution: A New Territory for the Strong Metal-Support Interaction Effect

HighlightsUltra-small and highly dispersed rhodium nanoparticles anchored in 2D ultra-thin boron nanosheets (BNS) were synthesized by a rapid NaBH4 reduction and facile freeze-dry approach.Due to the strong metal-support interaction effect, the optimized electrocatalyst exhibits excellent hydrogen evolution reaction (HER) catalytic activity and stability in the wide pH range electrolytes.Based on the stable surface, the oxidized boron surface facilitates the coupling of BNS and metal, giving catalyst outstanding HER performance.

The effects of SMSI on m-Cresol hydrodeoxygenation over Pt/Nb2O5 and Pt/TiO2

The hydrodeoxygenation (HDO) of m-cresol was studied on Pt/Nb2O5/MgAl2O4 and Pt/TiO2/MgAl2O4 catalysts to understand the effects of Strong Metal Support Interactions (SMSI). The Nb2O5 and TiO2 supports were prepared as 0.7-nm films on MgAl2O4 by Atomic Layer Deposition (ALD) to ensure that the structures of the catalyst were the same. When reduced at 773 K to place Pt in the encapsulated state, Pt/Nb2O5/MgAl2O4 was much less active than Pt/MgAl2O4 at 573 K but much more active at 623 K. While Pt/MgAl2O4 deactivated rapidly due to coking, Pt/Nb2O5/MgAl2O4 showed significantly better coke tolerance and was almost 100% selective towards toluene production. Pt/Nb2O5/MgAl2O4 reduced at lower temperatures exhibited intermediate catalytic properties. The effect of reduction temperature on Pt/TiO2/MgAl2O4 was much less and this catalyst was more similar to Pt/MgAl2O4 than its Nb2O5 counterpart. The implications of these results for understanding the nature of oxide promoters on HDO of m-cresol are discussed.

Crystal plane effect of ceria on supported copper catalyst for liquid-phase hydrogenation of unsaturated aldehyde

Ceria has been widely used as catalyst support displaying a size- or shape-dependent catalytic performance due to the strong metal-support interaction (SMSI) effect with active metal. Almost all the studies on the SMSI effect of ceria-supported metal catalysts are involved generally in gas-phase reaction, but rarely in the liquid-phase reaction system. In this work, Cu/CeO2-P (copper loaded on nano-polyhedral CeO2 with (111) terminated surface) was investigated its catalytic performance on liquid-phase hydrogenation and studied the SMSI effect by comparing with the catalysts supported on nano-rod and nano-cube CeO2. It was found that Cu was highly dispersed on the external surface of ceria in the Cu/CeO2-P catalyst via a moderate SMSI effect. Furthermore, the degree of the interaction showed great influence on the chemical state of Cu species, and the ratio of (Cu++Cu0)/Cu2+ in Cu/CeO2-P was higher than Cu/CeO2-R (Cu loaded on nano-rod CeO2 with (110) plane) and Cu/CeO2-C (Cu loaded on nano-cube CeO2 with (100) facet). As a result, the Cu/CeO2-P catalyst showed the best catalytic performance among three types of catalysts. Based on series of catalytic investigations, the catalytic performance in liquid-phase hydrogenation was intrinsically relevant to the crystal plane effect and reduced Cu proportion induced by an appropriate SMSI effect, which was completely different from gas-phase hydrogenation.

Synergistic catalysis of cluster and atomic copper induced by copper-silica interface in transfer-hydrogenation

To data, using strong metal-support interaction (SMSI) effect to improve the catalytic performance of metal catalysts is an important strategy for heterogeneous catalysis, and this effect is basically achieved by using reducible metal oxides. However, the formation of SMSI between metal and inert-support has been so little coverage and remains challenge. In this work, the SMSI effect can be effectively extended to the inert support-metal catalysis system to fabricate a Cu0/Cu-doped SiO2 catalyst with high dispersion and loading (38.5 wt.%) through the interfacial effect of inert silica. In the catalyst, subnanometric composite of Cu cluster and atomic copper (in the configuration of Cu-O-Si) can be consciously formed on the silica interface, and verified by extended X-ray absorption fine structure (EXAFS), in situ X-ray photoelectron spectroscopy (XPS), and high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) characterization. The promoting activity in transfer-hydrogenation by the SMSI effect of Cu-silica interface and the synergistic active roles of cluster and atomic Cu have also been revealed from surface interface structure, catalytic activity, and density functional theory (DFT) theoretical calculation at an atomic level. The subnanometric composite of cluster and atomic copper species can be derived from a facile synthesis strategy of metal-inert support SMSI effect and the realistic active site of Cu-based catalyst can also been identified accurately, thus it will help to expand the application of subnanometric materials in industrial catalysis.

A new choice of electrocatalyst carrier: Ni nanowires induced by magnetic field

The self-supporting electrocatalysts have been demonstrated more advantages than powder catalysts. Both metal-support interaction and support effect further exhibit that the substrate material has significant impact on the electrochemical performance of the catalysts. Herein, we introduce a nickel nanowires film (Ni-NNF), synthesized via hydrazine reduction under a magnetic field, as a conductive substrate. By comparing with common substrates (Ni foam, carbon cloth and carbon fiber paper), the as-fabricated Ni-NNF exhibits higher conductivity and provides more active sites, resulting in better hydrogen evolution reaction (HER) activities and excellent durability. Thus, employing this type of metal nanowires as substrate is expected to synthesize better electrocatalyst.

Metal-Loaded Hollow Carbon Nanostructures as Nanoreactors: Microenvironment Effects and Prospects for Biomass Hydrogenation Applications

Over the past decade, metal-loaded hollow carbon nanostructures have been hailed as man-made nanoreactors (MHC nanoreactors) for extensive applications in dealing with energy and environmental issues due to their tailorable structure and electronic properties. Unlike conventional reports of hollow nanostructures with regard to synthetic methodologies or structural properties, a distinctive viewpoint on the microenvironment effects of MHC nanoreactors, i.e., metal–support interaction effect, reactant enrichment effect, molecular sieving effect, spatial compartmentation effect, and metal stabilization effect, is highlighted herein from this perspective. Furthermore, to emphasize the great potential of MHC nanoreactors in constructing a sustainable energy system to achieve a greener modern lifestyle, a review of the applications of MHC nanoreactors in the hydrogenation of typical biomass-derived molecules is presented. Additionally, prospects for broader biomass valorization applications of MHC nanoreactors, i.e., in situ hydrogen source-assisted hydrogenation, hydrogenation-involved cascade-type reactions, hydrogenation product distribution modulation, stability prolongation and recyclability enhancement, are forecasted. Toward the end of this paper, some feasible suggestions are further proposed for the enhancement of the catalytic reactivity, selectivity, stability, and sustainability of MHC nanoreactors in biomass hydrogenation, with a sincere expectation to contribute to the development of a highly efficient biomass refining system.

Partially reduced Pd single atoms on CdS nanorods enable photocatalytic reforming of ethanol into high value-added multicarbon compound

<h2>Summary</h2> Photocatalytic co-production of high value-added multicarbon compounds and hydrogen from renewable bioethanol is an environmental and long-term approach to industrial activities and remains a great challenge because of the difficulty in bioethanol dehydrogenation. Guided by first-principle simulation, we first synthesized a partially reduced Pd–P₃ single atom (PdPSA) on CdS nanorods with an unoccupied hybrid state of Pd 4d and P 3p via both metal-support interaction effect and Pd–P coordination effect. This unique electronic structure of PdPSA is totally different from highly reduced S-coordinated Pd single atoms or nanoparticles and allows PdPSA-CdS to exhibit a visible-light photocatalytic activity of 35.1 mmol g⁻¹ h⁻¹ for the co-production of high-value-added 1,1-diethoxyethane and H₂ with a selectivity of 100%. Mechanism studies revealed that the unoccupied hybrid states of Pd 4d and P 3p in PdPSA not only greatly promoted the dehydrogenation of ethanol but also promised PdPSA with a high H₂-production activity.

Maximizing the Synergistic Effect of CoNi Catalyst on α-MoC for Robust Hydrogen Production.

We report the syntheses of highly dispersed CoNi bimetallic catalysts on the surface of α-MoC based on the strong metal support interaction (SMSI) effect. The interaction between the nearly atomically dispersed Co and Ni atoms was observed for the first time by the real-space chemical mapping at the atomic level. Combined with the ability of α-MoC to split water at low temperatures, the as-synthesized CoNi/α-MoC catalysts exhibited robust and synergistic performance for the hydrogen production from hydrolysis of ammonia borane. The metal-normalized activity of the bimetallic 1.5Co1.5Ni/α-MoC catalyst reached 321.1 molH2·mol-1CoNi·min-1 at 298 K, which surpasses all the noble metal-free catalysts ever reported and is four times higher than that of the commercial Pt/C catalyst.

Latest trends in Syngas production employing compound catalysts for methane dry reforming

The rise in the global population has ultimately steered to increase in global energy consumptions. This masqueraded several challenges worldwide. The most troublesome being the accumulation of greenhouse gases (GHGs) that induced a global climatic change. The utilization of fossil fuels like petroleum, coal and natural gas on the copious scale has led to the elevated levels of carbon dioxide (CO2) and methane (CH4) in the global environment. Dry reforming of methane (DRM) is a highly favorable technique as it utilizes two of the prominent GHGs, CH4 and CO2 to generate a useful and valuable product viz. syngas. However, the deactivation, coking and sintering of catalysts are still the main hurdles in the commercialization of the process. The compound metal catalysts have shown enhanced activity and prolonged durability when compared with monometallic catalysts due to enhanced morphology, improved and stable catalytic structure, i.e., both coke and sintering resistant at high temperatures. This brief review spotlights the recent developments in DRM by emphasizing parameters such as the effects of catalyst support, bimetallic catalyst, promoters and strong metal-support interaction (SMSI) in the last decade.

Enhancing the CO2 methanation activity of Ni/CeO2 via activation treatment-determined metal-support interaction

The metal-support interaction is of critical importance to enhance the catalytic activity and selectivity. However, it is still challenging to construct an appropriate interaction starting from the catalyst fabrication and/or activation. We herein established low-temperature treatment of Ni2+ ions impregnated on ceria in reductive atmosphere and reduction–oxidation cycles as effective approachs to regulate the metal-support interaction and raise the catalytic performance in the CO2 methanation. The proposed construction approach yielded Ni/CeO2 that displayed highly dispersed Ni nanoparticles in contact with CeO2 (111) and (100) facet, higher density of surface oxygen vacancies and larger amounts of weak basic sites relative to the reference samples, which increased the capacity for H2 and CO2 adsorption/activation. The interaction resulted in appreciably (2–3 fold) higher activity in the CO2 methanation with maintaining almost full selectivity to CH4 and high stability. Coverage of Ni surface by CeO2−x thin layer as a typical structure of strong metal-support interaction resulting from high-temperature reduction, can be alleviated via reduction–oxidation cycles. We also demonstrate the activation treatment-determined metal-support interaction effect can generally extend to (TiO2 and ZrO2) supported Ni catalysts.

Highly active and controllable MOF-derived carbon nanosheets supported iron catalysts for Fischer-Tropsch synthesis

N-doped carbon materials as catalyst supports have shown great superiority because of rich porosity, tunable metal-support interaction and electronic promotion effect. Controllable fabrication of carbon materials with specific morphology and different configurations provides wider possibilities for applications in catalysis. Herein, N-doped carbon nanosheets (CNS) were successfully synthesized by using monoclinic ZIF-8 nanosheets as templates. Compared with commercial active carbon and cubic ZIF-8 particles-derived carbon particles, the derived CNS exhibit superior graphitization degree and electronic effect. Consequently, the promoted Fe carburization improved the intrinsic activity for Fe/CNS catalysts in FTS. Further investigation on pyrolysis temperature achieved tunable configuration and content of N dopant. XPS, Raman, Mössbauer spectroscopy, TEM, H2-TPR etc. were combined to elucidate the promotion effect of CNS on dispersion, electronic properties and formation of Fe carbides. By correlating the composition and structure to catalytic performance in FTS, we illustrated the significance of carbon materials in Fe supported catalysts.

Synergistic Effect between Zr-MOF and Phosphomolybdic Acid with the Promotion of TiF4 Template.

Metal-Organic Framework (MOF) materials are often modified or functionalized, and then the crystal size and morphology of MOF materials are changed. In the process of preparing UiO-66 confined phosphomolybdic acid (PMA) composites (PU), the TiF4-modified PU (PMA + UiO-66) composite catalyst (TiF4-PU) was successfully synthesized by adding titanium tetrafluoride, and the catalytic desulfurization activity was excellent. Similarly, the reaction mechanism was investigated by means of infrared spectroscopy, Raman spectroscopy, XPS, and UV/Vis spectroscopy. The results show that the addition of TiF4 not only changes the appearance and color of the catalyst, but also changes the valence distribution of the elements in the catalyst. The number of oxygen vacancies in the MOF increases due to the addition of TiF4, and more electrons are transferred from the Zr-MOF to PMA to form more Mo5+, which improved the performance of oxidative desulfurization in comparison. Thus, a stronger strong metal-support interaction (SMSI) effect is observed for TiF4-modified PU catalysts. In addition, the quenching experiment of free radicals shows that ·OH radical is the main active substance in the oxidative desulfurization reaction over TiF4-PU catalyst.

Combing strong metal support interaction and N doping to improve the durability of 3D carbon nanosheets supported Pt catalyst

In this work, for the first time, MgFe2O4 (MFO) is used to stabilize the N-doped 3D carbon nanosheets supported platinum catalysts (Pt/MFO/NPC). The spherical MFO nanoparticles are randomly dispersed on the surface of the 3D carbon nanosheets, with Pt particles uniformly distributed on them. The Pt/MFO/NPC catalyst possesses excellent stability and methanol tolerance in alkaline solution. The current retention reaches 87.0% after 20,000 s of stability test, which is significantly higher than that of commercial Pt/C (46.9%). In addition, the onset potential (Eonset) and half-wave potential (E1/2) values of Pt/MFO/NPC are larger than that of the commercial contrast, implying the improved kinetics of the Oxygen reduction reaction (ORR). The excellent catalytic activity and stability of Pt/MFO/NPC can be attributed to the combined effect of N-doping and strong metal-support interaction (SMSI) between MFO and Pt.

Electronic Oxide-Metal Strong Interaction (EOMSI).

Strong metal-support interaction of supported metal catalysts is an important concept to describe the effect of metal-support interactions on the structures and catalytic performances of supported metal particles. By using an example of CeOx adlayers supported on Ag nanocrystals, herein a concept of electronic oxide-metal strong interaction (EOMSI) is put forward; this interaction significantly affects the electronic structures of oxide adlayers through metal-to-oxide charge transfer. The EOMSI can stabilize oxide adlayers in a low oxidation state under ambient conditions, which individually are not stable; moreover, the oxide adlayers experiencing the EOMSI are resistant to high-temperature oxidation in air to a certain extent. Such an EOMSI concept helps to generalize the strong influence of oxide-metal interactions on the structures and catalytic performance of oxide/metal inverse catalysts, which have been attracting increasing attention.

Reaction-Induced Strong Metal-Support Interactions between Metals and Inert Boron Nitride Nanosheets.

Encapsulation of metal nanocatalysts by support-derived materials is well known as a classical strong metal-support interaction (SMSI) effect that occurs almost exclusively with active oxide supports and often blocks metal-catalyzed surface reactions. In the present work this classical SMSI process has been surprisingly observed between metal nanoparticles, e.g., Ni, Fe, Co, and Ru, and inert hexagonal boron nitride (h-BN) nanosheets. We find that weak oxidizing gases such as CO2 and H2O induce the encapsulation of nickel (Ni) nanoparticles by ultrathin boron oxide (BOx) overlayers derived from the h-BN support (Ni@BOx/h-BN) during the dry reforming of methane (DRM) reaction. In-situ surface characterization and theory calculations reveal that surface B-O and B-OH sites in the formed BOx encapsulation overlayers work synergistically with surface Ni sites to promote the DRM process rather than blocking the surface reactions.

Hydrodechlorination and deep hydrogenation on single-palladium-atom-based heterogeneous catalysts

Halophenols are widely present in wastewater and groundwater, which threaten global water safety and human health. Importantly, hydrodechlorination (HDC) via heterogeneous catalysis is efficient and environmentally friendly. To further improve the catalytic performance and atomic economy, Pd-based single atom catalysts (SACs) were prepared through electrostatic attraction and used in the catalytic HDC for the first time. By substituting different defect-rich supports, the coordination environments of atomically dispersed Pd-atoms were mediated with different catalytic performance. The results demonstrate that the Pd/CeO2 SACs have the highest HDC activity and remain stable during cycle tests. The moderately intensive metal-support interactions (MIMSI) effect was identified as a critical factor for the higher activity of SACs, unlike the traditional strong metal-support interaction effect. The HDC process on Pd SACs was further investigated by combining kinetic experiments with density functional theory calculations, which facilitated the recognition of HDC intermediates and an understanding of the reaction mechanism.

Uniformly sized Pt nanoparticles dispersed at high loading on Titania nanotubes

A range of Pt loadings (0.9–21.5 wt. %) on titania nanotubes (TNT) catalysts were prepared with a view to address metal-support interaction effects on Pt nanoparticles (size, dispersion, shape) and were prepared by a vapor-phase impregnation method using Pt(acac). The reduced catalysts were characterized by XRD, TEM, H2-TPD, CO adsorption FTIR and examined as catalysts in naphthalene hydrogenation. Pt nanoparticles have a very uniform size between 1.4–2.2 nm for Pt loadings 0.9–21.5 wt% as indicated by TEM, H2-TPD and CO-adsorption FTIR. A strong metal-support interaction between Pt and TNT support hinder Pt nanoparticles to agglomerate into larger particles, even at high Pt loadings. Both Pt edge sites and exposed surface total Pt sites are highest at 10.2 wt.% Pt loading and parallels naphthalene hydrogenation activity which peaks at this loading.

Electrochemically Enhancing Nanostructured Fe-Oxide/Co3O4 for the Reverse Water Gas Shift Reaction

The abundant amount of CO2 in the atmosphere is a valuable resource that when managed correctly can replace energy from the fossil fuel industry and provide a carbon-neutral solution that will reduce the impacts of the climate and ecological crisis[1]. This is achieved by reducing CO2 with hydrogen (H2) through the reverse water gas shift (RWGS) reaction to produced carbon monoxide (CO). CO then acts as a source molecule in the Fischer-Tropsch synthesis to manufacture hydrocarbon fuels. Due to the high stability of the CO2 molecule, significant thermal energy is required to undertake the reaction. Iron-oxide (FeOx) has been shown to be an active and thermally stable catalysts towards the RWGS reaction. FeOx (iron-oxide) nanowires are fabricated through the polyol reduction method and have been characterized through scanning transmission electron microscopy (STEM) analysis[2]. Following the wet deposition method, the Fe nanowires are finely dispersed on cobalt-oxide (Co3O4) to act as a support and semi-conductor. The dispersion of Fe on Co3O4 enhances the electronic properties of the catalyst through the metal-support interaction (MSI) effect[3]. The MSI entails the back spillover of promoting oxygen (Oδ-) ionic species from Co3O4 to FeOx by an increase in temperature, altering the work function of FeOx and allowing to cycle oxygen from the breaking of CO2. Through the Electrochemical Promotion of Catalysis (EPOC) phenomenon the catalytic activity can be enhanced by altering the binding energy of the reactant and intermediate species on the catalytic surface[4]. The MSI and EPOC phenomena have been shown to be functionally equivalent in terms of the change in work function. The difference between them is that in EPOC the movement of ions can be controlled through the application of an electrical current or potential difference, while the MSI effect is controlled by a thermal input. EPOC entails the use of solid electrolytes, for instance yttria-stabilized zirconia (YSZ) and barium zirconate yttrium-doped (BZY) which are oxygen and proton conductors, respectively. The catalyst-working electrodes (i.e. FeOx nanowires) are deposited on one side of the electrolyte and on the opposite side, inert gold counter and reference electrodes. Through the application of a potential difference between the electrodes, promoting species migrate through the three-phase (solid-gas-catalyst) boundary in order to interact with the exposed-catalyst surface. In the case of BZY, when a potential difference is applied between the counter and working electrode, H+ are removed from the surface through the three-phase boundary (tpb) towards BZY, referred to as positive polarization. When the polarization is reversed from the working to counter electrode, H+ migrate from BZY through the tpb towards the catalytic surface. Utilizing YSZ, results in the opposite migration with O2- ions. Regardless of the type of solid electrolyte used the catalyst is oxidized under positive polarization and reduced under negative polarization. The use of the Co3O4 semiconductor allows to combine both the MSI and EPOC effect at 350°C, by finely dispersing the Fe nanowires on Co3O4 to expose active sites and lowering the rate of sintering while being conductive to close the circuit[5]. As opposed to using other supports that do not display fully conductive properties, this approach provides an electronic path for the promoters to follow. Results have shown the working-catalyst FeOx/Co3O4 on YSZ and BZY to be highly selective to CO formation under oxidizing (3CO2:H2) and reducing (CO2:7H2) conditions, with a superior activity experienced under rich reducing conditions. Furthermore, alteration in work function from the EPOC effect, has led to a promotional response for both YSZ and BZY. Combining the MSI and EPOC effect allows for high RWGS activity, establishing a promising solution in utilizing CO2 as a resource while using transition metals. Additionally, the EPOC effect will be elucidated through Fourier-Transform Infrared (FTIR) spectroscopy to provide insight on the promoting mechanism occurring during polarization. 1. Porosoff, M. D., Yan, B. & Chen, J. G. Catalytic reduction of CO2 by H2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities. Energy Environ. Sci. 2, 303 (2015).1. Baranova, E. A., Bock, C., Ilin, D., Wang, D. & MacDougall, B. Infrared spectroscopy on size-controlled synthesized Pt-based nano-catalysts. Surf. Sci. 600, 3502–3511 (2006).2. Panaritis, C., Edake, M., Couillard, M., Einakchi, R. & Baranova, E. A. Insight towards the role of ceria-based supports for reverse water gas shift reaction over RuFe nanoparticles. J. CO2 Util. 26, 350–358 (2018).3. Vayenas, C. G., Bebelis, S., Pliangos, C., Brosda, S. & Tsiplakides, D. Electrochemical Activation of Catalysis. (Springer US, 2001).4. Zagoraios, D. et al. Electrochemical promotion of methane oxidation over nanodispersed Pd/Co3O4 catalysts. Catal. Today (2019). doi:10.1016/j.cattod.2019.02.030