Advanced (photo)electrocatalytic approaches to substitute the use of fossil fuels in chemical production

Electrification of the chemical industry for carbon-neutral production requires innovative (photo)electrocatalysis. This study highlights the contribution and discusses recent research projects in this area, which are relevant case examples to explore new directions but characterised by a little background research effort. It is organised into two main sections, where selected examples of innovative directions for electrocatalysis and photoelectrocatalysis are presented. The areas discussed include (i) new approaches to green energy or H2 vectors, (ii) the production of fertilisers directly from the air, (iii) the decoupling of the anodic and cathodic reactions in electrocatalytic or photoelectrocatalytic devices, (iv) the possibilities given by tandem/paired reactions in electrocatalytic devices, including the possibility to form the same product on both cathodic and anodic sides to “double” the efficiency, and (v) exploiting electrocatalytic cells to produce green H2 from biomass. The examples offer hits to expand current areas in electrocatalysis to accelerate the transformation to fossil-free chemical production

Dynamics at polarized carbon dioxide-iron oxyhydroxide interfaces unveil the origin of multicarbon product formation

Surface-sensitive ambient pressure X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy combined with an electrocatalytic reactivity study, multilength-scale electron microscopy, and theoretical modeling provide insights into the gas-phase selective reduction of carbon dioxide to isopropanol on a nitrogen-doped carbon-supported iron oxyhydroxide electrocatalyst. Dissolved atomic carbon forms at relevant potentials for carbon dioxide reduction from the reduction of carbon monoxide chemisorbed on the surface of the ferrihydrite-like phase. Theoretical modeling reveals that the ferrihydrite structure allows vicinal chemisorbed carbon monoxide in the appropriate geometrical arrangement for coupling. Based on our observations, we suggest a mechanism of three-carbon-atom product formation, which involves the intermediate formation of atomic carbon that undergoes hydrogenation in the presence of hydrogen cations upon cathodic polarization. This mechanism is effective only in the case of thin ferrihydrite-like nanostructures coordinated at the edge planes of the graphitic support, where nitrogen edge sites stabilize these species and lower the overpotential for the reaction. Larger ferrihydrite-like nanoparticles are ineffective for electron transport

Interfacial chemistry in the electrocatalytic hydrogenation of CO2 over C‑supported Cu-based systems

Operando soft and hard X-ray spectroscopic techniques were used in combination with plane-wave density functional theory (DFT) simulations to rationalize the enhanced activities of Zn-containing Cu nanostructured electrocatalysts in the electrocatalytic CO2 hydrogenation reaction. We show that at a potential for CO2 hydrogenation, Zn is alloyed with Cu in the bulk of the nanoparticles with no metallic Zn segregated; at the interface, low reducible Cu­(I)–O species are consumed. Additional spectroscopic features are observed, which are identified as various surface Cu­(I) ligated species; these respond to the potential, revealing characteristic interfacial dynamics. Similar behavior was observed for the Fe–Cu system in its active state, confirming the general validity of this mechanism; however, the performance of this system deteriorates after successive applied cathodic potentials, as the hydrogen evolution reaction then becomes the main reaction pathway. In contrast to an active system, Cu­(I)–O is now consumed at cathodic potentials and not reversibly reformed when the voltage is allowed to equilibrate at the open-circuit voltage; rather, only the oxidation to Cu­(II) is observed. We show that the Cu–Zn system represents the optimal active ensembles with stabilized Cu­(I)–O; DFT simulations rationalize this observation by indicating that Cu–Zn–O neighboring atoms are able to activate CO2, whereas Cu–Cu sites provide the supply of H atoms for the hydrogenation reaction. Our results demonstrate an electronic effect exerted by the heterometal, which depends on its intimate distribution within the Cu phase and confirms the general validity of these mechanistic insights for future electrocatalyst design strategies

The Role of Substrate Surface Geometry in the Photo-Electrochemical Behaviour of Supported TiO₂ Nanotube Arrays: A Study Using Electrochemical Impedance Spectroscopy (EIS)

Highly ordered TiO2 nanotube (NT) arrays grown on Ti mesh and Ti foil were successfully prepared by a controlled anodic oxidation process and tested for water photo-electrolysis. Electrochemical impedance spectroscopy (EIS), combined with other electrochemical techniques (cyclic voltammetry and chronoamperometry) in tests performed in the dark and under illumination conditions, was used to correlate the photoactivity to the specific charge transfer resistances associated with a 3D (mesh) or 2D (foil) geometry of the support. The peculiar structure of the nanotubes in the mesh (with better light absorption and faster electron transport along the nanotubes) strongly impacts the catalytic performances under illumination. H2 production and current density in water photo-electrolysis were over three times higher with the TiO2NTs/Ti mesh, compared to the foil in the same conditions. The results obtained by the EIS technique, used here for the first time to directly compare TiO2 nanotubes on two different supports (Ti foil and Ti mesh), led to a better understanding of the electronic properties of TiO2 nanotubes and the effect of a specific support on its photocatalytic properties

Electrocatalytic reduction of CO2 over dendritic-type Cu- and Fe-based electrodes prepared by electrodeposition

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H2 production by selective photo-dehydrogenation of ethanol in gas and liquid phase on CuOx/TiO2 nanocomposites

CuOx/TiO2 nanocomposites prepared by copper photodeposition (1.0 and 2.5 wt% copper loading) on TiO2 (synthesized by three different routes) are studied in the ethanol photo-dehydrogenation in gas- and liquid-phase operations, and characterized in terms of surface area, phase composition by XRD, morphology and copper-oxide nanoparticle size distribution, and copper species by UV-visible diffuse reflectance spectroscopy. Cu2+ ions partially enter into the titania structure leading to the creation of oxygen vacancies responsible for the shift in the band gap, but also the creation of traps for photogenerated holes and electrons. While the band gap shifts to lower energies with the copper content, a maximum photocatalytic activity is shown for the intermediate copper loading. Gas-phase operations allow a higher H2 productivity with respect to liquid-phase operations, and especially a higher selectivity (about 92\u201393%) to acetaldehyde. It is remarked that the route of photo-dehydrogenation of ethanol to H2 and acetaldehyde has an economic value about 3.0\u20133.5 times higher than the alternative route of photoreforming to produce H2. Gas-phase operations would be preferable for the photo-dehydrogenation of ethanol

Water splitting on 3D-type meso/macro porous structured photoanodes based on Ti mesh

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