Catalyst degradation and product selectivity changes are two of the key challenges in the electrochemical reduction of CO2 on copper electrodes. Yet, these aspects are often overlooked. Here, we combine in situ X-ray spectroscopy, in situ electron microscopy, and ex situ characterization techniques to follow the long-term evolution of the catalyst morphology, electronic structure, surface composition, activity, and product selectivity of Cu nanosized crystals during the CO2 reduction reaction. We found no changes in the electronic structure of the electrode under cathodic potentiostatic control over time, nor was there any build-up of contaminants. In contrast, the electrode morphology is modified by prolonged CO2 electroreduction, which transforms the initially faceted Cu particles into a rough/rounded structure. In conjunction with these morphological changes, the current increases and the selectivity changes from value-added hydrocarbons to less valuable side reaction products, i.e., hydrogen and CO. Hence, our results suggest that the stabilization of a faceted Cu morphology is pivotal for ensuring optimal long-term performance in the selective reduction of CO2 into hydrocarbons and oxygenated products.
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 oxygen evolution reaction (OER) is crucial to future energy systems based on water electrolysis. Iridium oxides are promising catalysts due to their resistance to corrosion under acidic and oxidizing conditions. Highly active iridium (oxy)hydroxides prepared using alkali metal bases transform into low activity rutile IrO2 at elevated temperatures (>350 °C) during catalyst/electrode preparation. Depending on the residual amount of alkali metals, we now show that this transformation can result in either rutile IrO2 or nano-crystalline Li-intercalated IrOx. While the transition to rutile results in poor activity, the Li-intercalated IrOx has comparative activity and improved stability when compared to the highly active amorphous material despite being treated at 500 °C. This highly active nanocrystalline form of lithium iridate could be more resistant to industrial procedures to produce PEM membranes and provide a route to stabilize the high populations of redox active sites of amorphous iridium (oxy)hydroxides.
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.
We report a green, wet chemistry approach towards the production of C-supported Cu electrocatalysts active in the CO2 reduction to formic acid. We use citrus peels as a C support precursor and as a source of reducing agents for the Cu cations. We show that orange peel is a suitable starting material compared to lemon peel for the one-pot hydrothermal synthesis of Cu nanostructures affording better Cu dispersion as well as productivity and selectivity towards formic acid. We rationalize this finding in terms of the beneficial chemical composition of the orange peel, which favors both the reduction of the Cu precursor as well as the carbon matrix. This work demonstrates new viable opportunities for the reuse of citrus waste on a rational basis.
Stabilizing metal nanoparticles is vital for large scale implementations of supported metal catalysts, particularly for a sustainable transition to clean energy, e.g., H2 production. In this work, iridium sub-nanometric particles were deposited on commercial graphite and on graphitic carbon nitride by a wet impregnation method to investigate the metal-support interaction during the hydrous hydrazine decomposition reaction. To establish a structure-activity relationship, samples were characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The catalytic performance of the synthesized materials was evaluated under mild reaction conditions, i.e. 323 K and ambient pressure. The results showed that graphitic carbon nitride (GCN) enhances the stability of Ir nanoparticles compared to graphite, while maintaining remarkable activity and selectivity. Simulation techniques including Genetic Algorithm geometry screening and electronic structure analyses were employed to provide a valuable atomic level understanding of the metal-support interactions. N anchoring sites of GCN were found to minimise the thermodynamic driving force of coalescence, thus improving the catalyst stability, as well as to lead charge redistributions in the cluster improving the resistance to poisoning by decomposition intermediates.
The electrocatalytic conversion of CO2 to fuels and chemicals using renewable energy is a key decarbonization technology. From a technological viewpoint, the realization of such process in the gas phase and at room temperature is considered advantageous as it allows one to circumvent the limited CO2 solubility in liquid electrolytes and CO2 transport across the electrical double layer. Yet, electrocatalysts' performances reported so far are promising but not satisfactory. To inform the design of new materials, in this study, we apply ambient pressure X-ray photoelectron and absorption spectroscopies coupled with on-line gas detection via mass spectrometry to investigate in situ performance and interface chemistry of an electrodeposited Cu on graphitic carbon support under conditions of CO2 reduction. We use the ISISS beamline at the synchrotron facility BESSY II of the HZB and the electrochemical cell based on polymeric electrolyte membrane previously developed. We show that under cathodic potential in which methanol is formed, a fraction of the electrode with a predominantly Cu(I) electronic structure undergoes reduction to metallic Cu. The C speciation is characterized by C-O and sp3 CH3 species whereas no atomic C was formed under this condition. We also show the important role of water in the formation of methanol from accumulated surface CH3 species.
Photoelectron spectroscopy is a powerful characterisation tool for semiconductor surfaces and interfaces, providing in principle a correlation between the electronic band structure and surface chemistry along with quantitative parameters such as the electron affinity, interface potential, band bending and band offsets. However, measurements are often limited to ultrahigh vacuum and only the top few atomic layers are probed. The technique is seldom applied as an in situ probe of surface processing; information is usually provided before and after processing in a separate environment, leading to a reduction in reproducibility. Advances in instrumentation, in particular electron detection has enabled these limitations to be addressed, for example allowing measurement at near-ambient pressures and the in situ, real-time monitoring of surface processing and interface formation. A further limitation is the influence of the measurement method through irreversible chemical effects such as radiation damage during X-ray exposure and reversible physical effects such as the charging of low conductivity materials. For wide-gap semiconductors such as oxides and carbon-based materials, these effects can be compounded and severe. Here we show how real-time and near-ambient pressure photoelectron spectroscopy can be applied to identify and quantify these effects, using a gold alloy, gallium oxide and semiconducting diamond as examples. A small binding energy change due to thermal expansion is followed in real-time for the alloy while the two semiconductors show larger temperature-induced changes in binding energy that, although superficially similar, are identified as having different and multiple origins, related to surface oxygen bonding, surface band-bending and a room-temperature surface photovoltage. The latter affects the p-type diamond at temperatures up to 400 °C when exposed to X-ray, UV and synchrotron radiation and under UHV and 1 mbar of O2. Real-time monitoring and near-ambient pressure measurement with different excitation sources has been used to identify the mechanisms behind the observed changes in spectral parameters that are different for each of the three materials. Corrected binding energy values aid the completion of the energy band diagrams for these wide-gap semiconductors and provide protocols for surface processing to engineer key surface and interface parameters.
Platinum single-site catalysts (SSCs) are a promising technology for the production of hydrogen from clean energy sources. They have high activity and maximal platinum-atom utilization. However, the bonding environment of platinum during operation is poorly understood. In this work, we present a mechanistic study of platinum SSCs using operando, synchrotron-X-ray absorption spectroscopy. We synthesize an atomically dispersed platinum complex with aniline and chloride ligands onto graphene and characterize it with ex-situ electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, X-ray absorption near-edge structure spectroscopy (XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS). Then, by operando EXAFS and XANES, we show that as a negatively biased potential is applied, the Pt-N bonds break first followed by the Pt-Cl bonds. The platinum is reduced from platinum(II) to metallic platinum(0) by the onset of the hydrogen-evolution reaction at 0 V. Furthermore, we observe an increase in Pt-Pt bonding, indicating the formation of platinum agglomerates. Together, these results indicate that while aniline is used to prepare platinum SSCs, the single-site complexes are decomposed and platinum agglomerates at operating potentials. This work is an important contribution to the understanding of the evolution of bonding environment in SSCs and provides some molecular insights into how platinum agglomeration causes the deactivation of SSCs over time.
Photoelectron spectroscopy offers detailed information about the electronic structure and chemical composition of surfaces, owing to the short distance that the photoelectrons can escape from a dense medium. Unfortunately, photoelectron based spectroscopies are not directly compatible with the liquids required to investigate electrochemical processes, especially in the soft X-ray regime. To overcome this issue, different approaches based on photoelectron spectroscopy have been developed in our group over the last few years. The performance and the degree of information provided by these approaches are compared with those of the well established bulk sensitive spectroscopic approach of total fluorescence yield detection, where the surface information gained from this approach is enhanced using samples with large surface to bulk ratios. The operation of these approaches is exemplified and compared using the oxygen evolution reaction on IrOx catalysts. We found that all the approaches, if properly applied, provide similar information about surface oxygen speciation. However, using resonant photoemission spectroscopy, we were able to prove that speciation is more involved and complex than previously thought during the oxygen evolution reaction on IrOx based electrocatalysts. We found that the electrified solid-liquid interface is composed of different oxygen species, where the terminal oxygen atoms on iridium are the active species, yielding the formation of peroxo species and, finally, dioxygen as the reaction product. Thus, the oxygen-oxygen bond formation is dominated by peroxo species formation along the reaction pathway. Furthermore, the methodologies discussed here open up opportunities to investigate electrified solid-liquid interfaces in a multitude of electrochemical processes with unprecedented speciation capabilities, which are not accessible by one-dimensional X-ray spectroscopies.
Iridium and ruthenium and their oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotentials observed for Ru- and Ir-based anodes and the high corrosion resistance of Ir-oxides. Herein, by means of cutting edge operando surface and bulk sensitive X-ray spectroscopy techniques, specifically designed electrode nanofabrication and ab initio DFT calculations, we were able to reveal the electronic structure of the active IrOx centers (i.e., oxidation state) during electrocatalytic oxidation of water in the surface and bulk of high-performance Ir-based catalysts. We found the oxygen evolution reaction is controlled by the formation of empty Ir 5d states in the surface ascribed to the formation of formally IrV species leading to the appearance of electron-deficient oxygen species bound to single iridium atoms (µ1-O and µ1-OH) that are responsible for water activation and oxidation. Oxygen bound to three iridium centers (µ3-O) remains the dominant species in the bulk but do not participate directly in the electrocatalytic reaction, suggesting bulk oxidation is limited. In addition a high coverage of a µ1-OO (peroxo) species during the OER is excluded. Moreover, we provide the first photoelectron spectroscopic evidence in bulk electrolyte that the higher surface-to-bulk ratio in thinner electrodes enhances the material usage involving the precipitation of a significant part of the electrode surface and near-surface active species.
Revealing the active nature of oxide-derived copper is of key importance to understand its remarkable catalytic performance during the cathodic CO2 reduction reaction (CO2RR) to produce valuable hydrocarbons. Using advanced spectroscopy, electron microscopy, and electrochemically active surface area characterization techniques, the electronic structure and the changes in the morphology/roughness of thermally oxidized copper thin films were revealed during CO2RR. For this purpose, we developed an in situ cell for X-ray spectroscopy that could be operated accurately in the presence of gases or liquids to clarify the role of the initial thermal oxide phase and its active phase during the electrocatalytic reduction of CO2. It was found that the Cu(I) species formed during the thermal treatment are readily reduced to Cu0 during the CO2RR, whereas Cu(II) species are hardly reduced. In addition, Cu(II) oxide electrode dissolution was found to yield a porous/void structure, where the lack of electrical connection between isolated islands prohibits the CO2RR. Therefore, the active/stable phase for CO2RR is metallic copper, independent of its initial phase, with a significant change in its morphology upon its reduction yielding the formation of a rougher surface with a higher number of underco-ordinated sites. Thus, the initial thermal oxidation of copper in air controls the reaction activity/selectivity because of the changes induced in the electrode surface morphology/roughness and the presence of more undercoordinated sites during the CO2RR.
The ambient-pressure endstation and branchline of the Versatile Soft X-ray (VerSoX) beamline B07 at Diamond Light Source serves a very diverse user community studying heterogeneous catalysts, pharmaceuticals and biomaterials under realistic conditions, liquids and ices, and novel electronic, photonic and battery materials. The instrument facilitates studies of the near-surface chemical composition, electronic and geometric structure of a variety of samples using X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy in the photon energy range from 170â eV to 2800â eV. The beamline provides a resolving power hν/Δ(hν) > 5000 at a photon flux > 1010â photonsâ s-1 over most of its energy range. By operating the optical elements in a low-pressure oxygen atmosphere, carbon contamination can be almost completely eliminated, which makes the beamline particularly suitable for carbon K-edge NEXAFS. The endstation can be operated at pressures up to 100â mbar, whereby XPS can be routinely performed up to 30â mbar. A selection of typical data demonstrates the capability of the instrument to analyse details of the surface composition of solid samples under ambient-pressure conditions using XPS and NEXAFS. In addition, it offers a convenient way of analysing the gas phase through X-ray absorption spectroscopy. Short XPS spectra can be measured at a time scale of tens of seconds. The shortest data acquisition times for NEXAFS are around 0.5â s per data point.
The use of mechanochemistry to prepare catalytic materials is of significant interest; it offers an environmentally beneficial, solvent-free, route and produces highly complex structures of mixed amorphous and crystalline phases. This study reports on the effect of milling atmosphere, either air or argon, on mechanochemically prepared LaMnO3 and the catalytic performance towards N2O decomposition (deN2O). In this work, high energy resolution fluorescence detection (HERFD), X-ray absorption near edge structure (XANES), X-ray emission, and X-ray photoelectron spectroscopy (XPS) have been used to probe the electronic structural properties of the mechanochemically prepared materials. Moreover, in situ studies using near ambient pressure (NAP)-XPS, to follow the materials during catalysis, and high pressure energy dispersive EXAFS studies, to mimic the preparation conditions, have also been performed. The studies show that there are clear differences between the air and argon milled samples, with the most pronounced changes observed using NAP-XPS. The XPS results find increased levels of active adsorbed oxygen species, linked to the presence of surface oxide vacancies, for the sample prepared in argon. Furthermore, the argon milled LaMnO3 shows improved catalytic activity towards deN2O at lower temperatures compared to the air milled and sol-gel synthesised LaMnO3. Assessing this improved catalytic behaviour during deN2O of argon milled LaMnO3 by in situ NAP-XPS suggests increased interaction of N2O at room temperature within the O 1s region. This study further demonstrates the complexity of mechanochemically prepared materials and through careful choice of characterisation methods how their properties can be understood.
The variation in the morphology and electronic structure of copper during the electroreduction of CO2 into valuable hydrocarbons and alcohols was revealed by combining in situ surface- and bulk-sensitive X-ray spectroscopies with electrochemical scanning electron microscopy. These experiments proved that the electrified interface surface and near-surface are dominated by reduced copper. The selectivity to the formation of the key C-C bond is enhanced at higher cathodic potentials as a consequence of increased copper metallicity. In addition, the reduction of the copper oxide electrode and oxygen loss in the lattice reconstructs the electrode to yield a rougher surface with more uncoordinated sites, which controls the dissociation barrier of water and CO2. Thus, according to these results, copper oxide species can only be stabilized kinetically under CO2 reduction reaction conditions.
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.
The catalytic synthesis of NH3 from the thermodynamically challenging N2 reduction reaction under mild conditions is currently a significant problem for scientists. Accordingly, herein, we report the development of a nitrogenase-inspired inorganic-based chalcogenide system for the efficient electrochemical conversion of N2 to NH3, which is comprised of the basic structure of [Fe-S2-Mo]. This material showed high activity of 8.7 mgNH3 mgFe -1 h-1 (24 µgNH3 cm-2 h-1) with an excellent faradaic efficiency of 27% for the conversion of N2 to NH3 in aqueous medium. It was demonstrated that the Fe1 single atom on [Fe-S2-Mo] under the optimal negative potential favors the reduction of N2 to NH3 over the competitive proton reduction to H2. Operando X-ray absorption and simulations combined with theoretical DFT calculations provided the first and important insights on the particular electron-mediating and catalytic roles of the [Fe-S2-Mo] motifs and Fe1, respectively, on this two-dimensional (2D) molecular layer slab.
