Water Structure in the First Layers on TiO2: A Key Factor for Boosting Solar-Driven Water-Splitting Performances.

The water hydrogen-bonded network is strongly perturbed in the first layers in contact with the semiconductor surface. Even though this aspect influences the outer-sphere electron transfer, it was not recognized that it is a crucial factor impacting the solar-driven water-splitting performances. To fill this gap, we have selected two TiO2 anatase samples (with and without B-doping), and by extensive experimental and computational investigations, we have demonstrated that the remarkable 5-fold increase in water-splitting photoactivity of the B-doped sample cannot be ascribed to effects typically associated to enhanced photocatalytic properties, such as band gap, heterojunctions, crystal facets, and other aspects. Studying these samples by combining FTIR measurements under controlled humidity with first-principles simulations sheds light on the role and nature of the first-layer water structure in contact with the photocatalyst surfaces. It turns out that the doping hampers the percolation of tetrahedrally coordinated water molecules while enhancing the population of topological H-bond defects forming approximately linear H-bonded chains. This work unveils how doping the semiconductor surface affects the local electric field, determining the water splitting rate by influencing the H-bond topologies in the first water layers. This evidence opens new prospects for designing efficient photocatalysts for water splitting.

Understanding the complexity in bridging thermal and electrocatalytic methanation of CO2.

The selective methanation of CO2 is an important research area to meet the net-zero emission targets. Furthermore, it is crucial to develop solutions to achieve carbon neutrality, hydrogen utilization, carbon circularity, and chemical-energy storage. This conversion can be realized via the thermocatalytic multistep power-to-X route or by direct electro- (or photoelectro)-catalytic technologies. Herein, we discuss the need to accelerate direct technologies. Improving these technologies requires a better understanding of the catalytic chemistry and the complexity of the aspects to consider in bridging catalytic and electrocatalytic CO2 methanation. In this tutorial review, initially we analyze the fundamental question of the competitive adsorption of key reactants and regulation strategies to promote the overall reaction. Then, this approach is used to guide the reader in understanding the differences between thermocatalysis and electrocatalysis. Finally, the complexity of the aspects necessary to include in modelling and designing next-generation electrocatalysts for CO2 methanation is analyzed.

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.

Nanocarbon for Energy Material Applications: N2 Reduction Reaction.

Nanocarbons are an important class of energy materials and one relevant application is for the nitrogen reduction reaction, i.e., the direct synthesis of NH3 from N2 and H2 O via photo- and electrocatalytic approaches. Ammonia is also a valuable energy or hydrogen vector. This perspective paper analyses developments in the field, limiting discussion to nanocarbon-based electrodes. These aspects are discussed: i) active sites related to charge density differences on C atoms associated to defects/strains, ii) doping with heteroatoms, iii) introduction of isolated metal ions, iv) creation and in situ dynamics of metal oxide(hydroxide)/nanocarbon boundaries, and v) nanocarbon characteristics to control the interface. Discussion is focused on the performances and mechanistic aspects. Aim is not a systematic state-of-the-art report but to highlight the need to use a different perspective in studying this challenging reaction by using selected papers. Notwithstanding the large differences in the proposed nature of the active sites, fall all within a restricted range of performances, far from the targets. A holistic approach is emphasized to make a breakthrough advance.

Tuning the Chemical Properties of Co-Ti3 C2 Tx MXene Materials for Catalytic CO2 Reduction.

MXenes, a novel family of 2D materials, are energy materials that have gained considerable attention, particularly for their catalytic applications in emerging areas such as CO2 and N2 hydrogenation. Herein, for the first time, it is shown that the surface reducibility of Ti3 C2 Tx MXene can be tuned by N doping, which induces a change in the catalytic properties of supported Co nanoparticles. Pristine Co-Ti3 C2 Tx MXene favors CO production during CO2 hydrogenation, whereas CH4 production is favored when the MXene is subjected to simple N doping. X-ray photoelectron spectroscopy and transmission electron microscopy (TEM) reveal that surface rutile TiO2 nanoparticles appear on the Ti3 C2 Tx support upon N doping, which interact strongly with the supported Co nanoparticles. This interaction alters the reducibility of the supported Co nanoparticles at the interface with the TiO2 nanoparticles, shifting the product selectivity from CO to CH4 . This study successfully showcases a practical strategy, based on surface chemistry modulation of 2D MXenes, for regulating product distribution in CO2 hydrogenation.

Elucidating the mechanism of the CO2 methanation reaction over Ni-Fe hydrotalcite-derived catalysts via surface-sensitive in situ XPS and NEXAFS.

Hydrotalcite-derived Ni and Fe-promoted hydrotalcite-derived Ni catalysts were found to outperform industrial catalysts in the CO2 methanation reaction, however the origin of the improved activity and selectivity of these catalysts is not clear. Here, we report a study of these systems by means of in situ X-ray photoelectron spectroscopy and near-edge X-ray absorption spectroscopy elucidating the chemical nature of the catalysts surface under reaction conditions and revealing the mechanism by which Fe promotes activity and selectivity towards methane. We show that the increase of the conversion leads to hydroxylation of the Ni surface following the formation of water during the reaction. This excessive Ni surface hydroxylation has however a detrimental effect as shown by a controlled study. A dominant metallic Ni surface exists in conditions of higher selectivity towards methane whereas if an increase of the Ni surface hydroxylation occurs, a higher selectivity towards carbon monoxide is observed. The electronic structure analysis of the Fe species under reaction conditions reveals the existence of predominantly Fe(iii) species at the surface, whereas a mixture of Fe(ii)/Fe(iii) species is present underneath the surface when selectivity to methane is high. Our results highlight that Fe(ii) exerts a beneficial effect on maintaining Ni in a metallic state, whereas the extension of the Fe oxidation is accompanied by a more extended Ni surface hydroxylation with a negative impact on the selectivity towards methane.

Comparing Molecular Mechanisms in Solar NH3 Production and Relations with CO2 Reduction.

Molecular mechanisms for N2 fixation (solar NH3) and CO2 conversion to C2+ products in enzymatic conversion (nitrogenase), electrocatalysis, metal complexes and plasma catalysis are analyzed and compared. It is evidenced that differently from what is present in thermal and plasma catalysis, the electrocatalytic path requires not only the direct coordination and hydrogenation of undissociated N2 molecules, but it is necessary to realize features present in the nitrogenase mechanism. There is the need for (i) a multi-electron and -proton simultaneous transfer, not as sequential steps, (ii) forming bridging metal hydride species, (iii) generating intermediates stabilized by bridging multiple metal atoms and (iv) the capability of the same sites to be effective both in N2 fixation and in COx reduction to C2+ products. Only iron oxide/hydroxide stabilized at defective sites of nanocarbons was found to have these features. This comparison of the molecular mechanisms in solar NH3 production and CO2 reduction is proposed to be a source of inspiration to develop the next generation electrocatalysts to address the challenging transition to future sustainable energy and chemistry beyond fossil fuels.

Catalysis by hybrid sp2/sp3 nanodiamonds and their role in the design of advanced nanocarbon materials.

Hybrid sp2/sp3 nanocarbons, in particular sp3-hybridized ultra-dispersed nanodiamonds and derivative materials, such as the sp3/sp2-hybridized bucky nanodiamonds and sp2-hybridized onion-like carbons, represent a rather interesting class of catalysts still under consideration. Their characteristics, properties and catalytic reactivity are presented, with an analysis of the state-of-the-art of their use in gas- and liquid-phase reactions, including photo- and electro-catalysis. It is remarked that intrinsic differences exist between these and other nanostructured carbon catalysts. The analysis shows how different features make nanocarbons unique with respect to other types of catalysts and are the bases for an advanced design of nanocarbon-type catalysts. The aspects discussed regard the presence of hybrid sp2/sp3 configurations, nano-engineering related to the role of defects and vacancies in their catalytic behaviour, the creation of active sites by modification in the charge density at carbon atoms or C-C bonds, the generation of strained C-C bonds by curvature and other mechanisms, and the formation of semiconducting areas and defect sites at the interface with supported nanoparticles. The advanced strategies for identifying and quantifying active sites of carbon catalysts are highlighted.

Waste to Chemicals for a Circular Economy.

The implementation of a circular economy is a fundamental step to create a greater and more sustainable future for a better use of resources and energy. Wastes and in particular municipal solid waste represent an untapped source of carbon (and hydrogen) to produce a large range of chemicals from methane to alcohols (as methanol or ethanol) or urea. The waste to chemical process and related economics are assessed in this concept article to show the validity of such solution both from an economic point of view and from an environmental perspective considering the sensible reduction in greenhouse gas emissions with respect to conventional production from fossil fuels.

Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst.

Ammonia is synthesized directly from water and N2 at room temperature and atmospheric pressure in a flow electrochemical cell operating in gas phase (half-cell for the NH3 synthesis). Iron supported on carbon nanotubes (CNTs) was used as the electrocatalyst in this half-cell. A rate of ammonia formation of 2.2×10-3  gNH3 m-2 h-1 was obtained at room temperature and atmospheric pressure in a flow of N2 , with stable behavior for at least 60 h of reaction, under an applied potential of -2.0 V. This value is higher than the rate of ammonia formation obtained using noble metals (Ru/C) under comparable reaction conditions. Furthermore, hydrogen gas with a total Faraday efficiency as high as 95.1 % was obtained. Data also indicate that the active sites in NH3 electrocatalytic synthesis may be associated to specific carbon sites formed at the interface between iron particles and CNT and able to activate N2 , making it more reactive towards hydrogenation.

CO2 utilization: an enabling element to move to a resource- and energy-efficient chemical and fuel production.

CO(2) conversion will be at the core of the future of low-carbon chemical and energy industry. This review gives a glimpse into the possibilities in this field by discussing (i) CO(2) circular economy and its impact on the chemical and energy value chain, (ii) the role of CO(2) in a future scenario of chemical industry, (iii) new routes for CO(2) utilization, including emerging biotechnology routes, (iv) the technology roadmap for CO(2) chemical utilization, (v) the introduction of renewable energy in the chemical production chain through CO(2) utilization, and (vi) CO(2) as a suitable C-source to move to a low-carbon chemical industry, discussing in particular syngas and light olefin production from CO(2). There are thus many stimulating possibilities offered by using CO(2) and this review shows this new perspective on CO(2) at the industrial, societal and scientific levels.

Catalysis for biomass and CO2 use through solar energy: opening new scenarios for a sustainable and low-carbon chemical production.

The use of biomass, bio-waste and CO2 derived raw materials, the latter synthesized using H2 produced using renewable energy sources, opens new scenarios to develop a sustainable and low carbon chemical production, particularly in regions such as Europe lacking in other resources. This tutorial review discusses first this new scenario with the aim to point out, between the different possible options, those more relevant to enable this new future scenario for the chemical production, commenting in particular the different drivers (economic, technological and strategic, environmental and sustainability and socio-political) which guide the selection. The case of the use of non-fossil fuel based raw materials for the sustainable production of light olefins is discussed in more detail, but the production of other olefins and polyolefins, of drop-in intermediates and other platform molecules are also analysed. The final part discusses the role of catalysis in establishing this new scenario, summarizing the development of catalysts with respect to industrial targets, for (i) the production of light olefins by catalytic dehydration of ethanol and by CO2 conversion via FTO process, (ii) the catalytic synthesis of butadiene from ethanol, butanol and butanediols, and (iii) the catalytic synthesis of HMF and its conversion to 2,5-FDCA, adipic acid, caprolactam and 1,6-hexanediol.

Catalysis for Carbon-Circularity: Emerging Concepts and Role of Inorganic Chemistry.

Carbon circularity is crucial for achieving a circular economy but has wider implications and impacts with respect to the circularity of materials. It has an in-depth transformative effect on the economy. CO2 recycling is a critical component for this objective, with catalysis and inorganic chemistry playing a determining role in achieving this challenge. This concept paper presents some examples, as food for thought, of unconventional aspects in developing thermal and electro/photocatalysts for recycling CO2. The aspects discussed regard designing novel materials for CO2 thermo- or electro-conversion and developing novel nanostructured electrodes.

The Still Elusive Role of Lightweight Doping in Carbon-Based Electrocatalysts for the Selective Oxygen Reduction Reaction to Hydrogen Peroxide.

The two-electron electrocatalytic oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2) is a valuable alternative to the more conventional and energy-intensive anthraquinone process. From a circularity viewpoint, metal-free catalysts constitute a sustainable alternative for the process. In particular, lightweight hetero-doped C-materials are cost-effective and easily scalable samples that replace - more and more frequently - the use of critical raw elements in the preparation of highly performing (electro)catalysts. Anyhow, their large-scale exploitation in industrial processes still suffers from technical limits of samples upscale and reproducibility other than a still moderate comprehension of their action mechanism in the process. This concept article offers a comprehensive and exhaustive "journey" through the most representative lightweight hetero-doped C-based electrocatalysts and their performance in the 2e- ORR process. It provides an interpretation of phenomena at the triple-phase interface of solid catalyst, liquid electrolyte and gaseous oxygen based on the doping-driven generation of ideal electronic microenvironments at the catalyst surface.

High photocatalytic yield in the non-oxidative coupling of methane using a Pd-TiO2 nanomembrane gas flow-through reactor.

The photocatalytic non-oxidative coupling of methane (NOCM) is a highly challenging and sustainable reaction to produce H2 and C2+ hydrocarbons under ambient conditions using sunlight. However, there is a lack of knowledge, particularly on how to achieve high photocatalytic yield in continuous-flow reactors. To address this, we have developed a novel flow-through photocatalytic reactor for NOCM as an alternative to the conventionally used batch reactors. Me/TiO2 photocatalysts, where Me = Au, Ag and Pd, are developed, but only those based on Pd are active. Interestingly, the preparation method significantly impacts performance, going from inactive samples (prepared by wet impregnation) to highly active samples (prepared by strong electrostatic adsorption - SEA). These photocatalysts are deposited on a nanomembrane, and the loading effect, which determines productivity, selectivity, and stability, is also analysed. Transient absorption spectroscopy (TAS) analysis reveals the involvement of holes and photoelectrons after charge separation on Pd/TiO2 (SEA) and their interaction with methane in ethane formation, reaching a production rate of about 1000 µmol g-1 h-1 and a selectivity of almost 95% after 5 hours of reaction. Stability tests involving 24 h of continuous irradiation are performed, showing changes in productivity and selectivity to ethane, ethylene and CO2. The effect of a mild oxidative treatment (80 °C) to extend the catalyst's lifetime is also reported.

Correction to "Interfacial Chemistry in the Electrocatalytic Hydrogenation of CO2 over C-Supported Cu-Based Systems".

[This corrects the article DOI: 10.1021/acscatal.3c01288.].

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.

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.

Across the Board: Gabriele Centi on Decoupling Electrocatalytic Reactions to Electrify Chemical Production.

In this series of articles, the board members of ChemSusChem discuss recent research articles that they consider of exceptional quality and importance for sustainability. This entry features Prof. G. Centi, who discusses the decoupling of the electrocatalytic reactions to realize spatiotemporal separation of the anodic and cathodic processes using redox mediators. This solution allows to potentially overcome the limitations due to intermittency of renewable energy production, besides a series of other advantages such as an improved energy efficiency.