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Perovskite LaCoO3 is being increasingly explored as an effective low-cost electrocatalyst for the oxygen evolution reaction (OER). Sr doping in LaCoO3 (La1−xSrxCoO3) has been found to substantially increase its catalytic activity. In this work, we report a detailed study on the evolution of the electronic structure of La1−xSrxCoO3 with 0 ≤ x ≤ 1 and its correlation with electrocatalytic activity for the OER. A combination of X-ray photoemission spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) was used to unravel the electronic density of states (DOS) near the Fermi level (EF), which provide insights into the key electronic structure features for the enhanced OER catalytic activity. Detailed analysis on the Co L-edge XAS suggest that LaCoO3 has a low spin state with t2g6eg0 configuration at room temperature. This implies that the high OER catalytic activity of LaCoO3 should not be rationalized by the occupancy of eg = 1 descriptor. Substituting Sr2+ for La3+ in LaCoO3 induces Co4+ oxidation states and effectively dopes hole states into the top of valence band. A semiconductor-to-metal transition is observed for × ≥ 0.2, due to the hole-induced electronic DOS at the EF and increased hybridization between Co 3d and O 2p. Such an electronic modulation enhances the surface adsorption of the *OH intermediate and reduces the energy barrier for interfacial charge transfer, thus improving the OER catalytic activity in La1−xSrxCoO3. In addition, we found that the La1−xSrxCoO3 surface undergoes amorphization after certain period of OER measurement, leading to a partial deactivation of the electrocatalyst. High Sr doping levels accelerated the amorphization process.

The presence of defects and chemical dopants in metal-free carbon materials plays an important role in the electrocatalysis of the oxygen reduction reaction (ORR). The precise control and design of defects and dopants in carbon electrodes will allow the fundamental understanding of activity-structure correlations for tailoring catalytic performance of carbon-based, most particularly graphene-based, electrode materials. Herein, we adopted monolayer graphene – a model carbon-based electrode – for systematical introduction of nitrogen and oxygen dopants, together with vacancy defects, and studied their roles in catalyzing ORR. Compared to pristine graphene, nitrogen doping exhibited a limited effect on ORR activity. In contrast, nitrogen doping in graphene predoped with vacancy defects or oxygen enhanced the activities at 0.4 V vs the reversible hydrogen electrode (RHE) by 1.2 and 2.0 times, respectively. The optimal activity was achieved for nitrogen doping in graphene functionalized with oxygenated defects, 12.8 times more than nitrogen-doped and 7.7 times more than pristine graphene. More importantly, oxygenated defects are highly related to the 4e– pathway instead of nitrogen dopants. This work indicates a non-negligible contribution of oxygen and especially oxygenated vacancy defects for the catalytic activity of nitrogen-doped graphene.

Nanostructured tin oxide (SnO2) is a very promising electron transport layer (ETL) for perovskite solar cells (PSCs) that allows low-temperature processing in the planar n–i–p architecture. However, minimizing current–voltage (J–V) hysteresis and optimizing charge extraction for PSCs in this architecture remains a challenge. In response to this, we study and optimize different types of single- and bilayer SnO2 ETLs. Detailed characterization of the optoelectronic properties reveals that a bilayer ETL composed of lithium (Li)-doped compact SnO2 (c(Li)-SnO2) at the bottom and potassium-capped SnO2 nanoparticle layers (NP-SnO2) at the top enhances the electron extraction and charge transport properties of PSCs and reduces the degree of ion migration. This results in an improved PCE and a strongly reduced J–V hysteresis for PSCs with a bilayer c(Li)-NP-SnO2 ETL as compared to reference PSCs with a single-layer or undoped bilayer ETL. The champion PSC with c(Li)-NP-SnO2 ETL shows a high stabilized PCE of up to 18.5% compared to 15.7%, 12.5% and 16.3% for PSCs with c-SnO2, c(Li)-SnO2 and c-NP-SnO2 as ETL, respectively.

International audience; At the nanoscale, the properties of materials depend critically on the presence of crystal defects. However, imaging and characterising the structure of defects in three dimensions inside a crystal remain a challenge. Here, by using Bragg coherent diffraction imaging, we observe an unexpected anomalous {110} glide plane in two Pt sub-micrometer crystals grown by very different processes and having very different morphologies. The structure of the defects (type, associated glide plane and lattice displacement) is imaged in these faceted Pt crystals. Using this non-invasive technique both plasticity and unusual defect behaviour can be probed at the nanoscale.

The novel material class of high entropy oxides with their unique and unexpected physicochemical properties is a candidate for energy applications. Herein, it is reported for the first time about the physico‐ and (photo‐) electrochemical properties of ordered mesoporous (CoNiCuZnMg)Fe2O4 thin films synthesized by a soft‐templating and dip‐coating approach. The A‐site high entropy ferrites (HEF) are composed of periodically ordered mesopores building a highly accessible inorganic nanoarchitecture with large specific surface areas. The mesoporous spinel HEF thin films are found to be phase‐pure and crack‐free on the meso‐ and macroscale. The formation of the spinel structure hosting six distinct cations is verified by X‐ray‐based characterization techniques. Photoelectron spectroscopy gives insight into the chemical state of the implemented transition metals supporting the structural characterization data. Applied as photoanode for photoelectrochemical water splitting, the HEFs are photostable over several hours but show only low photoconductivity owing to fast surface recombination, as evidenced by intensity‐modulated photocurrent spectroscopy. When applied as oxygen evolution reaction electrocatalyst, the HEF thin films possess overpotentials of 420 mV at 10 mA cm−2 in 1 m KOH. The results imply that the increase of the compositional disorder enhances the electronic transport properties, which are beneficial for both energy applications.

Although zinc oxide (ZnO) is one of the most commonly used materials for electron transport layers in organic solar cells (OSCs), it also comes with disadvantages such as the so‐called light‐soaking issues, i.e., its need for exposure to UV light to reach its full potential in OSCs. Here, the impact of ZnO light‐soaking issues on stability measurements of OSCs is investigated. It is found that in the absence of UV light a reversible degradation occurs, which is independent of the used active layer material and accelerates at higher temperatures but can be undone with a short UV exposure. This reversible aging is attributed to the re‐adsorption of oxygen, which for manufacturing reasons is trapped at the interface of ZnO, even in an oxygen‐free environment. This oxygen can be removed with a UV pretreatment of the ZnO but at the expense of device efficiency and production that has to take place in an oxygen‐free environment. This study establishes that stability measurements of ZnO‐containing OSCs must be performed exclusively with a light source including a UV part since the usage of a simple white light source – as often reported in the literature – can lead to erroneous results.

Intensity of photocurrent during water oxidation in BiVO4 is predominantly limited by charge transfer resistance (Rct), rather than semiconductor bulk resistance (Rbulk). Mo doping of BiVO4 can slightly reduce Rbulk but obviously decreases Rct.

Interfaces are key elements that define electronic properties of the final device. Inevitably, most of the active interfaces of III–V semiconductor devices are buried and it is therefore not straightforward to characterize them. The Tapered Cross Section Photoelectron Spectroscopy (TCS‐PES) approach is promising to address such a challenge. That the TCS‐PES can be used to study the relevant heterojunction in epitaxial III–V architectures prepared by metalorganic chemical vapor deposition is demonstrated here. A MULTIPREP polishing system that enables controlling the angle between the sample holder and the polishing plate has been employed to improve the reproducibility of the polishing procedure. With this procedure, that preparing the TCS of III–V semiconductor devices with tapering angles lower than 0.02° is possible is demonstrated. The PES provides then information about the buried interfaces of Ge|GaInP and GaAs|GaInP layer stacks. Both, chemical and electronic properties have been measured by PES. It evidences that the preparation of the TCSs under an uncontrolled atmosphere modifies the pristine properties of the critical buried heterointerfaces. Surface states and reaction layers are created on the TCS surface, which restrict unambiguous conclusions on buried interface energetics.

Despite the great potential of metal-organic frameworks (MOFs) in catalysis, industrial applications are still scarce. This is mainly due to a lack of performance when changing from idealized lab conditions towards realistic conditions of the actual application. In this work, we demonstrate the applicability and outstanding catalytic performance of an alumina-supported [Pd(2-pymo)2]n MOF catalyst in the selective hydrogenation of acetylene to ethylene under industrial front-end conditions. It shows a competitive performance to an industrial benchmark catalyst and even exceeds it in terms of ethane selectivity due to the combination of well-defined isolated Pd active sites and synergies due to MOF-support-interactions. The high stability was proven for up to 60 h time-on-stream and supported by XPS and XRD structural analysis.

Carbon supported metallic nanomaterials are of great interest due to their low-cost, high durability and promising functional performance. Herein, a highly active oxygen evolution reaction (OER) electrocatalyst comprised of defective carbon shell encapsulated metal (Fe, Co, Ni) nanoparticles and their alloys supported on in-situ formed N-doped graphene/carbon nanotube hybrid is synthesized from novel single-source-precursors (SSP). The precursors are synthesized by a facile one-pot reaction of tannic acid with polyethylenimine and different metal ions and subsequent pyrolysis of the SSP. Benefiting from the heteroatom doping of carbon and formation of well-encapsulated metal/alloy nanoparticles, the obtained FeNi@NC-900 catalyst possesses lowest overpotentials of 310 mV to achieve a current density of 10 mA cm

Oxygen vacancies (OVs) have been reported to significantly alter the photocatalytic properties of BiOCl nanosheets. However, their formation mechanism and their role in the enhancement of photoelectrochemical performance remain unclear. In this work, thermally induced oxygen vacancies are introduced in BiOCl nanosheets by annealing in He atmosphere at various temperatures and their formation mechanism is investigated by in-situ diffuse reflectance infrared (DRIFTS) measurements. The influence of OVs on band offset, carrier concentrations and photoelectrochemical performance are systematically studied. The results show that (1) the surface of BiOCl nanosheets is extremely sensitive to temperature and defects are formed at temperatures as low as 200 degrees C in inert atmosphere. (2) The formation of surface and bulk OVs in BiOCl is identified by a combination of XPS, in-situ DRIFTS, and EPR experiments. (3) The photocurrent of BiOCl is limited by the concentration of charge carriers and shallow defect states induced by bulk oxygen vacancies, while the modulation of these parameters can effectively increase light absorption and carrier concentration leading to an enhancement of photoelectrochemical performance of BiOCl.

For driving the (photo-) electrocatalytic water splitting reaction both efficient and photostable absorber materials and electrocatalysts are needed in order to make the technology economically competitive. The novel material class of high entropy oxides with their unique and unexpected physicochemical properties is a potential candidate for energy applications. Herein, we report for the first time about the physico- and (photo-) electrochemical properties of ordered mesoporous (CoNiCuZnMg)Fe2O4 thin films synthesized by a soft-templating and dip-coating approach. The high entropy ferrites (HEF) are composed of 15 ‒ 18 nm sized and periodically ordered mesopores building a highly accessible inorganic nanoarchitecture with specific surface areas up to 170 m2/g. The mesoporous HEF thin films crystallize in the cubic spinel structure and were found to be crack-free on the meso- and macroscale. The formation of the spinel structure hosting six distinct cations was verified by means of gracing incidence X-ray diffraction, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and transmission electron microscopy accompanied with energy dispersive X-ray spectroscopy. Photoelectron spectroscopy gave insight into chemical state of the implemented transition metals supporting the structural characterization data. Analyzed as photoanode for photoelectrochemical water splitting, the HEFs showed only low photoconductivity owing to fast surface recombination as suggested by intensity-modulated photocurrent spectroscopy. When applied as oxygen evolution reaction electrocatalyst, the HEF thin films possess overpotentials of 420 mV vs. RHE at 10 mA/cm2 in 1 M KOH. The results imply that the increase of the configurational disorder within the spinel structure enhances the electronic transport properties. The evaluation of the energy band alignment by Mott-Schottky analysis allows for an estimation which redox reactions can be driven, showing that the materials are theoretically capable of promoting overall water splitting.

The electrochemical nitrogen reduction reaction (NRR) to ammonia (NH

Stable InP (001) surfaces are characterized by fully occupied and empty surface states close to the bulk valence and conduction band edges, respectively. The present photoemission data show, however, a surface Fermi level pinning only slightly below the midgap energy which gives rise to an appreciable surface band bending. By means of density functional theory calculations, it is shown that this apparent discrepancy is due to surface defects that form at finite temperature. In particular, the desorption of hydrogen from metalorganic vapor phase epitaxy grown P-rich InP (001) surfaces exposes partially filled P dangling bonds that give rise to band gap states. These defects are investigated with respect to surface reactivity in contact with molecular water by low-temperature water adsorption experiments using photoemission spectroscopy and are compared to our computational results. Interestingly, these hydrogen-related gap states are robust with respect to water adsorption, provided that water does not dissociate. Because significant water dissociation is expected to occur at steps rather than terraces, surface band bending of a flat InP (001) surface is not affected by water exposure.

Despite the extensive ongoing research on MoS2 field effect transistors(FETs), the key role of device processing conditions in the chemistry involved at the metalto-MoS2 interface and their influence on the electrical performance are often overlooked. In addition, the majority of reports on MoS2 contacts are based on exfoliated MoS2, whereas synthetic films are even more susceptible to the changes made in device processing conditions. In this paper, working FETs with atomic layer deposition (ALD)-based MoS2 films and Ti/Au contacts are demonstrated, using current−voltage (I−V) characterization. In pursuit of optimizing the contacts, high-vacuum thermal annealing as well as O2/Ar plasmacleaning treatments are introduced, and their influence on the electrical performance is studied. The electrical findings are linked to the interface chemistry through X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM) analyses. XPS evaluation reveals that the concentration of organic residues on the MoS2 surface, as a result of resist usage during the device processing, is significant. Removal of these contaminations with O2/Ar plasma changes the MoS2 chemical state and enhances the MoS2 electrical properties. Based on the STEM analysis, the observed progress in the device electrical characteristics could also be associated with the formation of a continuous TiSx layer at the Ti-to-MoS2 interface. Scaling down the Ti interlayer thickness and replacing it with Cr is found to be beneficial as well, leading to further device performance advancements. Our findings are of value for attaining optimal contacts to synthetic MoS2 films

Graphene as a two-dimensional material is prone to hydrocarbon contaminations, which can significantly alter its intrinsic electrical properties. Herein, we implement a facile hydrogenation-dehydrogenation strategy to remove hydrocarbon contaminations and preserve the excellent transport properties of monolayer graphene. Using electron microscopy we quantitatively characterized the improved cleanness of hydrogenated graphene compared to untreated samples. In situ spectroscopic investigations revealed that the hydrogenation treatment promoted the adsorption ofytyt water at the graphene surface, resulting in a protective layer against the re-deposition of hydrocarbon molecules. Additionally, the further dehydrogenation of hydrogenated graphene rendered a more pristine-like basal plane with improved carrier mobility compared to untreated pristine graphene. Our findings provide a practical post-growth cleaning protocol for graphene with maintained surface cleanness and lattice integrity to systematically carry a range of surface chemistry in the form of a well-performing and reproducible transistor.

ACS sustainable chemistry & engineering 9(18), 6235-6249 (2021). doi:10.1021/acssuschemeng.0c08760, Published by ACS Publ., Washington, DC

Electrochemical water splitting is a process to store renewable energy in hydrogen, which is a green energy carrier producing only water when combusted. However, the overall electrochemical water splitting is limited by the low efficiency of the anodic oxygen evolution reaction (OER) leading to a high overpotential. In this study, finely dispersed cobalt particles supported on graphene are prepared as an anodic catalyst and coupled with phosphate activation to enhance and stabilize OER activity. The small particles enable a high exposure of the surface active sites. Also, the highly conductive graphene backbone accelerates electron transport. Activation by phosphate in the electrolyte leads to the formation of the active Co(iii) species with enriched oxygen vacancies meanwhile facilitating the kinetics. The finely dispersed cobalt particles supported on graphene together with phosphate activation lead to high electrochemical surface area and intrinsic activity, achieving a current density of 10 mA cm−2at an overpotential of 0.35 V and a low Tafel slope of 45 mV per decade, together with good stability. The cobalt mass based current density is 19-8000 times higher than current benchmarking catalysts.

Transition metal phosphides have been recognized as efficient co-catalysts to boost the activity of semiconductor photocatalysts. However, a rigorous and quantitative understanding is still to be developed about how transition metal phosphides influence photoexcited electron dynamics. Here, we present a nanosecond time-resolved transient absorption spectroscopy (TAS) study of the photoexcited electron dynamics in carbon nitrides (g-C3N4) before and after Co and/or P modifications. Our spectroscopic study showed that Co or P lowered the initial electron density, whereas they promoted the photoexcited electron relaxation of g-C3N4, with their half-life times (t50%) of 2.5 and 1.8 ns, respectively. The formation of a CoP co-catalyst compound promoted the electron relaxation (t50%=2.8 ns) without significantly lowering the charge separation efficiency. Density functional theory (DFT) calculations were undertaken to explore the underlying fundamental reasons and they further predicted that CoP, compared to Co or P modification, better facilitates photoexcited electron transfer from g-C3N4 to reactants.

Oxygen evolution reaction (OER) electrocatalysts suitable to work in acid are typically restricted to platinum group noble metal oxides because of their high activity and, especially, stability. Co3O4 is currently explored as an alternative OER catalyst. Herein we prepared Co3O4 films on fluorine-doped Sn oxide (FTO) glass and Ti foil via thermal decomposition of nitrate salts and evaluated their activity and stability in 0.05 M H2SO4. Crystalline Co3O4 films deposited on FTO were stable during chronopotentiometry at 10 mA cm−2 for over 16 hours. The dissolution rate was 61 ngCo cm−2 min−1. The choice of a stable support such as FTO is essential to ensure the stability of the catalyst-substrate interface and to prevent substrate passivation under OER conditions. Doping Co3O4 with Li resulted in a higher OER activity under acidic conditions to be attributed to the larger electrochemical surface area, although the stability was impeded compared to undoped Co3O4.

Solid sorbents are essential for developing technologies that directly capture CO

CuBi2O4 exhibits significant potential for the photoelectrochemical (PEC) conversion of solar energy into chemical fuels, owing to its extended visible-light absorption and positive flat band potential vs the reversible hydrogen electrode. A detailed understanding of the fundamental electronic structure and its correlation with PEC activity is of significant importance to address limiting factors, such as poor charge carrier mobility and stability under PEC conditions. In this study, the electronic structure of CuBi2O4 has been studied by a combination of hard X-ray photoemission spectroscopy, resonant photoemission spectroscopy, and X-ray absorption spectroscopy (XAS) and compared with density functional theory (DFT) calculations. The photoemission study indicates that there is a strong Bi 6s-O 2p hybrid electronic state at 2.3 eV below the Fermi level, whereas the valence band maximum (VBM) has a predominant Cu 3d-O 2p hybrid character. XAS at the O K-edge supported by DFT calculations provides a good description of the conduction band, indicating that the conduction band minimum is composed of unoccupied Cu 3d-O 2p states. The combined experimental and theoretical results suggest that the low charge carrier mobility for CuBi2O4 derives from an intrinsic charge localization at the VBM. Also, the low-energy visible-light absorption in CuBi2O4 may result from a direct but forbidden Cu d-d electronic transition, leading to a low absorption coefficient. Additionally, the ionization potential of CuBi2O4 is higher than that of the related binary oxide CuO or that of NiO, which is commonly used as a hole transport/extraction layer in photoelectrodes. This work provides a solid electronic basis for topical materials science approaches to increase the charge transport and improve the photoelectrochemical properties of CuBi2O4-based photoelectrodes.

The key to fully leveraging the potential of the electrochemical CO2 reduction reaction (CO2RR) to achieve a sustainable solar‐power‐based economy is the development of high‐performance electrocatalysts. The development process relies heavily on trial and error methods due to poor mechanistic understanding of the reaction. Demonstrated here is that ionic liquids (ILs) can be employed as a chemical trapping agent to probe CO2RR mechanistic pathways. This method is implemented by introducing a small amount of an IL ([BMIm][NTf2]) to a copper foam catalyst, on which a wide range of CO2RR products, including formate, CO, alcohols, and hydrocarbons, can be produced. The IL can selectively suppress the formation of ethylene, ethanol and n‐propanol while having little impact on others. Thus, reaction networks leading to various products can be disentangled. The results shed new light on the mechanistic understanding of the CO2RR, and provide guidelines for modulating the CO2RR properties. Chemical trapping using an IL adds to the toolbox to deduce the mechanistic understanding of electrocatalysis and could be applied to other reactions as well.

NiFe-(oxy)hydroxide is one of the most active electrocatalysts for the oxygen evolution reaction (OER) in alkaline conditions. Herein we investigated the stability of NiFe-(oxy)hydroxide anodes at high current densities (100 mA cm−2) at different temperatures (25, 75 °C) and base concentrations (1, 5, 10 M KOH). While polarization led to minor structural and compositional changes under standard conditions (25 °C, 1 M KOH), the anodes were severely impacted at higher temperature (75 °C) and base concentrations (5, 10 M KOH). Overall leaching and preferential leaching of Fe (resulting in a lower Fe/Ni ratio) led to decreased OER performance and increased charge transfer resistance for the samples tested at industrially relevant conditions. A dramatic loss in the catalytic activity occurred for the sample polarized at 75 °C in 10 M KOH: besides extensive leaching, a transformation of Ni(OH)2 into NiO was noted in this case. For pure NiOxHy, incorporation of Fe impurities from the electrolyte during polarization at 75 °C in 5 M KOH led to an improvement in the catalytic activity and charge-transfer properties, approaching the performance of NiFeOxHy.

Electroless plating is a powerful tool in nanofabrication and is available for many of the noble transition metals. There is, however, a striking lack of electroless plating procedures for the rarer platinum-group metals. In this work, two plating baths for nanoscale iridium coatings are developed and their conformality and nanofabrication potential are showcased by coating ion-track-etched polycarbonate membranes, creating Ir nanotubes in the process. Both plating solutions yield morphologically different deposits, indicating that the microstructure of the film can be tuned by adjusting the composition of the plating bath. The catalytic performance of the deposited materials is investigated by using membrane-embedded nanotubes as catalysts for the reduction of 4-nitrophenol and methyl orange by borohydride, showing remarkable activity and stability. Operation in flow-through configuration, in which the metallized membrane is implemented as a microreactor greatly enhances the interaction with the catalyst surface, considerably increasing product yield. The results highlight the potential of Ir nanoplating for realizing sophisticated nanostructures and heterogeneous catalysts, but also illustrate the intricacies related to the complex chemistry of electroless Ir plating baths.

The dual factual and ethical dimension of learning in geography calls for consideration of how pupils in schools handle this complexity and how teachers might promote the development of ethical dec...