Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates.

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple overlapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (∼0.34 eV/monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O2 evolution onset coincide due to weaker binding and destabilization (∼0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

Facile and Eco-Friendly Approach To Produce Confined Metal Cluster Catalysts.

Zeolite-supported metal nanocluster catalysts have attracted significant attention due to their broad application in heterogeneously catalyzed reactions. The preparation of highly dispersed metal catalysts commonly involves the use of organic compounds and requires the implementation of complicated procedures, which are neither green nor deployable at the large scale. Herein, we present a novel facile method (vacuum-heating) which employs a specific thermal vacuum processing protocol of catalysts to promote the decomposition of metal precursors. The removal of coordinated H2O via vacuum-heating restricts the formation of intermediates (metal-bound OH species), resulting in catalysts with a uniform, metal nanocluster distribution. The structure of the intermediate was determined by in situ Fourier transform infrared, temperature-programmed decomposition, and X-ray absorption spectroscopy (XAS) measurements. This alternative synthesis method is eco-friendly and cost-effective as the procedure occurs in the absence of organic compounds. It can be widely used for the preparation of catalysts from different metal species (Ni, Fe, Cu, Co, Zn) and precursors and is readily scaled-up.

On the effect of metal loading on the reducibility and redox chemistry of ceria supported Pd catalysts.

The effect of Pd loading on the redox characteristics of a ceria support was examined using in situ Pd K-edge XAS, Ce L3-edge XAS and in situ X-ray diffraction techniques. Analysis of the data obtained from these techniques indicates that the onset temperature for the partial reduction of Ce(IV) to Ce(III), by exposure to H2, varies inversely with the loading of Pd. Whilst the onset and completion temperatures of the reduction of Ce(IV) to Ce(III) are different, both samples yield the same maximal fraction of Ce(III) formation independent of Pd loading. Furthermore, the partial reduction of Ce is found to be concurrent with the reduction of PdO and demonstrated that the presence of metallic Pd is necessary for the reduction of the CeO2 support. Upon passivation by room temperature oxidation, a full oxidation of the reduced ceria support was observed. However, only a mild surface oxidation of Pd was identified. The mild passivation of the Pd is found to lead to a highly reactive sample upon a second reduction by H2. The onset of the reduction of Pd and Ce has been demonstrated to be independent of the Pd loading after a mild passivation with both samples exhibiting near room temperature reduction in the presence of H2.

Elucidation of copper environment in a Cu-Cr-Fe oxide catalyst through in situ high-resolution XANES investigation.

Copper containing materials are widely used in a range of catalytic applications. Here, we report the use of Cu K-edge high resolution XANES to determine the local site symmetry of copper ions during the thermal treatment of a Cu-Cr-Fe oxide catalyst. We exploited the Cu K-edge XANES spectral features, in particular the correlation between area under the pre-edge peak and its position to determine the local environment of Cu2+ ions. The information gained from this investigation rules out the presence of Cu2+ ions in a tetrahedral or square planar geometry, a mixture of these sites, or in a reduced oxidation state. Evidence is presented that the Cu2+ ions in the Cu-Cr-Fe oxide system are present in a distorted octahedral environment.

Temperature reversible synergistic formation of cerium oxyhydride and Au hydride: a combined XAS and XPDF study.

In situ studies on the physical and chemical properties of Au in inverse ceria alumina supported catalysts have been conducted between 295 and 623 K using high energy resolved fluorescence detection X-ray absorption near edge spectroscopy and X-ray total scattering. Precise structural information is extracted on the metallic Au phase present in a 0.85 wt% Au containing inverse ceria alumina catalyst (ceria/Au/alumina). Herein evidence for the formation of an Au hydride species at elevated temperature is presented. Through modelling of total scattering data to extract the thermal properties of Au using Grüneisen theory of volumetric thermal expansion it proposed that the Au Hydride formation occurs synergistally with the formation of a cerium oxyhydride. The temperature reversible nature, whilst remaining in a reducing atmosphere, demonstrates the activation of hydrogen without consumption of oxygen from the supporting ceria lattice.

High-Pressure Study of the Elpasolite Perovskite La2NiMnO6.

Here we report a high-pressure investigation into the structural and magnetic properties of the double perovskite La2NiMnO6 using neutron scattering over a temperature range of 4.2-300 K at ambient pressure and over a temperature range of 120-1177 K up to a maximum pressure of 6.6 GPa. X-ray diffraction was also used up to a maximum pressure of 64 GPa, over a temperature range of 300-720 K. The sample was found to exist in a mixed rhombohedral/monoclinic symmetry at ambient conditions, the balance of which was found to be strongly temperature- and pressure-dependent. Alternating current magnetometry and X-ray absorption near-edge structure measurements were made at ambient pressure to characterize the sample, suggesting that the transition-metal sites exist in a mixed Ni3+/Mn3+ and Ni2+/Mn4+ state at ambient temperature and pressure. Analysis of the magnetic properties of the sample shows that the Curie temperature can be enhanced by ∼12 K with 2 GPa applied pressure, but it is highly stable at pressures beyond this. We report a pressure-volume-temperature equation of state for this material over this combined temperature and pressure range, with an ambient temperature bulk modulus of ∼179(8) GPa. The previously reported transition from monoclinic to rhombohedral symmetry upon heating to 700 K is seen to be encouraged with applied pressure, transforming fully by ∼1.5 GPa. Raman spectroscopy data were collected up to ∼8 GPa and show no clear changes or discontinuities over the reported phase transition to rhombohedral symmetry or any indication of further changes over the range considered. The ambient-pressure Grüneisen parameter γth was determined to be γth = 2.6 with a Debye temperature of 677 K. The individual modal parameters γj at ambient temperature were also determined from the high-pressure Raman data.

Structure of Nano-sized CeO2 Materials: Combined Scattering and Spectroscopic Investigations.

The structure of several nano-sized ceria, CeO2 , systems was investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction and total pair distribution functions (PDFs) revealed that in all of the samples the occupancy of both Ce4+ and O2- are very close to the ideal stoichiometry, the analysis using Reverse Monte Carlo technique revealed significant disorder around oxygen atoms in the nano-sized ceria samples in comparison to the highly crystalline NIST standard. In addition, the analysis revealed that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributable to the particle size of the CeO2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L3 - and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, is attributed to differences in particle size.

Rutile to anatase phase transition induced by N doping in highly oriented TiO2 films.

Highly oriented TiO2 thin films were deposited onto Al2O3(0001), SrTiO3(001), and LaAlO3(001) substrates by spin coating a titanium alkoxide precursor solution followed by annealing. The films were nitrogen doped by two different routes: either by adding tetramethyethylenediamine (TMEDA) to the precursor solution or alternatively by high temperature ammonolysis. Undoped TiO2 films were highly oriented and the phase was dependent on the substrate. N doping by ammonolysis led to transformation of rutile films to anatase, confirmed by XRD and by XPS valence band spectroscopy. Significant differences were observed in the spatial distribution of the nitrogen dopant depending upon which synthesis method was used. These two factors may shed light on the increased photocatalytic efficiencies reported in N doped TiO2.

Energy-resolved electron-yield XAS studies of nanoporous CoAlPO-18 and CoAlPO-34 catalysts.

Energy-resolved electron-yield X-ray absorption spectroscopy is a promising technique for probing the near-surface structure of nanomaterials because of its ability to discriminate between the near-surface and bulk of materials. So far, the technique has only been used in model systems. Here, the local structural characterization of nanoporous cobalt-substituted aluminophosphates is reported and it is shown that the technique can be employed for the study of open-framework catalytically active systems. Evidence that the cobalt ions on the surface of the crystals react differently to those in the bulk is found.

Local structure and speciation of platinum in fresh and road-aged North American sourced vehicle emissions catalysts: an X-ray absorption spectroscopic study.

Given emerging concerns about the bioavailability and toxicity of anthropogenic platinum compounds emitted into the environment from sources including vehicle emission catalysts (VEC), the platinum species present in selected North American sourced fresh and road-aged VEC were determined by Pt and Cl X-ray absorption spectroscopy. Detailed analysis of the Extended X-ray Absorption Fine Structure at the Pt L3 and L2 edges of the solid phase catalysts revealed mainly oxidic species in the fresh catalysts and metallic components dominant in the road-aged catalysts. In addition, some bimetallic components (Pt-Ni, Pt-Pd, Pt-Rh) were observed in the road-aged catalysts from supporting Ni-, Pd-, and Rh-K edge XAS studies. These detailed analyses allow for the significant conclusion that this study did not find any evidence for the presence of chloroplatinate species in the investigated solid phase of a Three Way Catalyst or Diesel Oxidation Catalysts.

Single-step co-deposition of nanostructured tungsten oxide supported gold nanoparticles using a gold-phosphine cluster complex as the gold precursor.

The use of a molecular gold organometallic cluster in chemical vapour deposition is reported, and it is utilized, together with a tungsten oxide precursor, for the single-step co-deposition of (nanostructured) tungsten oxide supported gold nanoparticles (NPs). The deposited gold-NP and tungsten oxide supported gold-NP are highly active catalysts for benzyl alcohol oxidation; both show higher activity than SiO2 supported gold-NP synthesized via a solution-phase method, and tungsten oxide supported gold-NP show excellent selectivity for conversion to benzaldehyde.

What are the active species in the photoinduced H2 production with terpyridyl Pt(II) complexes? An investigation by in situ XAFS.

Origin of the species: In situ X-ray absorption measurements show that monomeric Pt(II) species are the active components for photocatalytic H2 evolution under visible-light illumination for both [PtCl(tpy)]Cl on its own and a three-component system comprising Ru(bpy)3Cl2, MV(2+) and [PtCl(tpy)]Cl in the presence of a sacrificial electron donor (EDTA).

Elucidation of structure and nature of the PdO-Pd transformation using in situ PDF and XAS techniques.

The PdO-Pd phase transformation in a 4 wt% Pd/Al2O3 catalyst has been investigated using in situ X-ray absorption spectroscopy (XAS) and in situ X-ray total scattering (also known as high-energy X-ray diffraction) techniques. Both the partial and total pair distribution functions (PDF) from these respective techniques have been analysed in depth. New information from PDF analysis of total scattering data has been garnered using the differential PDF (d-PDF) approach where only correlations orginating from PdO and metallic Pd are extracted. This method circumvents problems encountered in characerising the catalytically active components due to the diffuse scattering from the disordered γ-Al2O3 support phase. Quantitative analysis of the palladium components within the catalyst allowed for the phase composition to be established at various temperatures. Above 850 °C it was found that PdO had converted to metallic Pd, however, the extent of reduction was of the order ca. 70% Pd metal and 30% PdO. Complementary in situ XANES and EXAFS were performed, with heating to high temperature and subsequent cooling in air, and the results of the analyses support the observations, that residual PdO is detected at elevated temperatures. Hysteresis in the transformation upon cooling is confirmed from XAS studies where reoxidation occurs below 680 °C.

Structure and speciation of chromium ions in chromium doped Fe2O3 catalysts.

In this paper, we report a detailed characterisation of chromium doped iron oxide catalysts using a range of techniques to establish the nature of chromium species in the near surface and bulk of iron oxide, high-temperature shift (HTS) catalysts. In particular we have employed X-ray absorption spectroscopy Cr K-edge near edge and extended fine structure data for comparison with chemical and X-ray photoelectron spectroscopy. There was excellent agreement between the techniques in terms of identification and quantification of Cr(6+) and Cr(3+) species as a function of calcination temperatures between 100 and 500 °C.

Tracking the structural changes in pure and heteroatom substituted aluminophosphate, AIPO-18, using synchrotron based X-ray diffraction techniques.

We report the structural changes that occur during the thermal removal of organic template molecules that occlude the pores of small pore nanoporous zeolitic solids, AlPO-18, SAPO-18, CoAlPO-18, ZnAlPO-18 and CoSAPO-18. The calcination process is a necessary step in the formation of active catalysts. The studies performed using time-resolved High Resolution Powder Diffraction (HRPD) and High Energy X-ray Diffraction (HEXRD) techniques at various temperatures reveal that changes that take place are dependent on the type of heteroatom present in the nanoporous solids. While time-resolved HRPD shows clear changes in lattice parameters during the removal of physisorbed water molecules and subsequent removal of the organic template, HEXRD data show changes in various near neighbour distances in AlPO-18, SAPO-18, CoAlPO-18, CoSAPO-18 and ZnAlPO-18 during the calcination process. In particular HEXRD reveals the presence of water molecules coordinated to Al(III) ions in the as-synthesised materials. Upon removal of the template and water, these solids show contraction in the cell volume at elevated temperatures while first and second neighbour distances remained almost unchanged.

Surface charge as activity descriptors for electrochemical CO2 reduction to multi-carbon products on organic-functionalised Cu.

Intensive research in electrochemical CO2 reduction reaction has resulted in the discovery of numerous high-performance catalysts selective to multi-carbon products, with most of these catalysts still being purely transition metal based. Herein, we present high and stable multi-carbon products selectivity of up to 76.6% across a wide potential range of 1 V on histidine-functionalised Cu. In-situ Raman and density functional theory calculations revealed alternative reaction pathways that involve direct interactions between adsorbed histidine and CO2 reduction intermediates at more cathodic potentials. Strikingly, we found that the yield of multi-carbon products is closely correlated to the surface charge on the catalyst surface, quantified by a pulsed voltammetry-based technique which proved reliable even at very cathodic potentials. We ascribe the surface charge to the population density of adsorbed species on the catalyst surface, which may be exploited as a powerful tool to explain CO2 reduction activity and as a proxy for future catalyst discovery, including organic-inorganic hybrids.

Facile Solution Process of VO2 Film with Mesh Morphology for Enhanced Thermochromic Performance.

The fabrication and applications of VO2 film continue to be of considerable interest due to their good thermochromic performance for smart windows. However, low visible transmittance (Tlum) and solar modulation efficiency (∆Tsol) impede the application of VO2 film, and they are difficult to improve simultaneously. Here, a facile zinc solution process was employed to control the surface structure of dense VO2 film and the processed VO2 film showed enhanced visible transmittance and solar modulation efficiency, which were increased by 7.5% and 9.5%, respectively, compared with unprocessed VO2 film. This process facilitated the growth of layered basic zinc acetate (LBZA) nanosheets to form mesh morphology on the surface of VO2 film, where LBZA nanosheets enhance the visible transmittance as an anti-reflection film. The mesh morphology also strengthened the solar modulation efficiency with small caves between nanosheets by multiplying the times of reflection. By increasing the zinc concentration from 0.05 mol/L to 0.20 mol/L, there were more LBZA nanosheets on the surface of the VO2 film, leading to an increase in the solar/near-infrared modulation efficiency. Therefore, this work revealed the relationship between the solution process, surface structure, and optical properties, and thus can provide a new method to prepare VO2 composite film with desirable performance for applications in smart windows.

Monitoring the process of formation of ZnO from ZnO2usingin situcombined XRD/XAS technique.

Use ofin situcombined x-ray diffraction and x-ray absorption spectroscopy for the study of the thermal decomposition of zinc peroxide to zinc oxide is reported here. Comparison of data extracted from both x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) with thermo gravimetric analysis (TGA) enabled us to follow the nature of the conversion of ZnO2to ZnO. A temperature range between 230 °C and 350 °C appears to show that a very poorly crystalline ZnO is formed prior to the formation of an ordered ZnO material. Both the decrease in white line intensity in the Zn K-edge XANES and resulting lower coordination numbers estimated from analysis of the Zn K-edge data of ZnO heated at 500 °C, in comparison to bulk ZnO, suggest that the ZnO produced by this method has significant defects in the system.

Catalytic reaction mechanism of Mn-doped nanoporous aluminophosphates for the aerobic oxidation of hydrocarbons.

In this work we apply state-of-the-art electronic-structure-based computational methods based on hybrid-exchange density functional theory to study the mechanism of the aerobic oxidation of hydrocarbons catalysed by Mn-doped nanoporous aluminophosphates (Mn-AlPOs). We compare our results with available experimental data. We show that the catalytic efficiency of Mn-AlPOs in oxidation reactions is intrinsically linked to 1) the Mn redox activity, in particular between 2+ and 3+ oxidation states, and 2) the coordinative insaturation of tetrahedral Mn embedded in AlPO frameworks, which facilitates the reaction by stabilising oxo-type radicals through the formation of Mn complexes. Our mechanism demonstrates the crucial role of both Mn(III) and Mn(II) in the reaction mechanism: Mn(III) sites undergo an initial reaction cycle that leads to the production of the alkyl hydroperoxide intermediate, which can only be transformed into the oxidative products (alcohol, aldehyde and acid) by Mn(II). A preactivation step is required to yield the reduced Mn(II) sites able to decompose the hydroperoxide intermediates; this step takes place through a transformation of the hydrocarbon into the corresponding peroxo-derivative, stabilised by forming a complex with Mn(III) and yielding at the same time reduced Mn(II) sites. Both species enter a subsequent propagation cycle in which Mn(II) catalyses the dissociation of the hydroperoxide that proceeds until the formation of the oxidative products by two parallel pathways, through alkoxy- or hydroxy-radical-like intermediates, whilst the Mn(III)-peroxo complex enables further production of the hydroperoxide intermediate.

A novel route for the inclusion of metal dopants in silicon.

We report a new method for introducing metal atoms into silicon wafers, using negligible thermal budget. Molecular thin films are irradiated with ultra-violet light releasing metal species into the semiconductor substrate. Secondary ion mass spectrometry and x-ray absorption spectroscopy show that Mn is incorporated into Si as an interstitial dopant. We propose that our method can form the basis of a generic low-cost, low-temperature technology that could lead to the creation of ordered dopant arrays.