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Green and highly selective synthesis of organonitrogen chemicals (ONCs) using the renewable energy source biomass over noble-metal free solid catalysts under common room temperature and pressure conditions is still a major challenge. Here, we report a sustainable electrochemical method for selective synthesis of several valuable ONCs with high yields using biomass-derived furanic aldehydes over greenly fabricated TiS2 nanosheets through a facile synthesis. Based on a range of characterization techniques including high-resolution transmission electron microscopy and X-ray absorption fine structure, a well-defined structure of the TiS2 nanosheets (3.86 nm with 1T phase) was constructed. These as-prepared catalysts were applied to the electrochemical reductive amination (ERA) of three biomass-derived aldehydes, i.e. furfural (FF), 5-methylfurfural (MF) and 5-hydroxymethylfurfural (HMF), and exhibited superior performance whereby over 95% conversion of each furanic aldehyde and nearly perfect selectivity of ONCs were achieved. TiS2 nanosheets, in particular, exhibited a marked ∼2-fold increase in conversion (∼49%) compared with the monometallic Ti electrode. Besides, the reaction kinetics and rational pathway were also studied. In addition, these exfoliated TiS2 nanosheets maintained high durability over 6 h, providing a promising and versatile route for the sustainable upgrading of biomass-derived sources. [ABSTRACT FROM AUTHOR]

We demonstrate a modified sol‐immobilization procedure using (MeOH)x/(H2O)1‐x solvent mixtures to prepare Pd/TiO2 catalysts that are able to reduce the formation of acid catalyzed products, e. g. ethers, for the hydrogenation of furfural. Transmission electron microscopy found a significant increase in polyvinyl alcohol (PVA) deposition at the metal‐support interface and temperature programmed reduction found a reduced uptake of hydrogen, compared to an established Pd/TiO2 preparation. We propose that the additional PVA hinders hydrogen spillover onto the TiO2 support and limits the formation of Brønsted acid sites, required to produce ethers. Elsewhere, the new preparation route was able to successfully anchor colloidal Pd to the TiO2 surface, without the need for acidification. This work demonstrates the potential for minimizing process steps as well as optimizing catalyst selectivity – both important objectives for sustainable chemistry. [ABSTRACT FROM AUTHOR]

We have made high surface area catalysts for the selective oxidation of methanol to formaldehyde. This is done in two ways – (i) by doping haematite with Al ions, to increase the surface area of the material, but which itself is unselective and (ii) by surface coating with Mo which induces high selectivity. Temperature programmed desorption (TPD) of methanol shows little difference in surface chemistry of the doped haematite from the undoped material, with the main products being CO2 and CO, but shifted to somewhat higher desorption temperature. However, when Mo is dosed onto the haematite surface, the chemistry changes completely to show mainly the selective product, formaldehyde, with no CO2 production, and this is little changed up to 10% Al loading. But at 15 wt% Al, the chemistry changes to indicate the presence of a strongly acidic function at the surface, with additional dimethyl ether and CO/CO2 production characteristic of the presence of alumina. Structurally, X-ray diffraction (XRD) shows little change over the range 0–20% Al doping, except for some small lattice contraction, while the surface area increases from around 20 to 100 m2 g−1. Using X-ray absorption spectroscopy (XAS) it is clear that, at 5% loading, the Al is incorporated into the Fe2O3 corundum lattice, which has the same structure as α-alumina. By 10% loading then it appears that the alumina starts to nano-crystallise within the haematite lattice into the γ form. At higher loadings, there is evidence of phase separation into separate Al-doped haematite and γ-alumina. If we add 1 monolayer equivalent of Mo to the surface there is already high selectivity to formaldehyde, but little change in structure, because that monolayer is isolated at the surface. However, when three monolayers equivalent of Mo is added, we then see aluminium molybdate type signatures in the XANES spectra at 5% Al loading and above. These appear to be in a sub-surface layer with Fe molybdate, which we interpret as due to Al substitution into ferric molybdate layers immediately beneath the topmost surface layer of molybdena. It seems like the separate γ-alumina phase is not covered by molybdena and is responsible for the appearance of the acid function products in the TPD. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We demonstrate a modified sol‐immobilization procedure using (MeOH)x/(H2O)1‐x solvent mixtures to prepare Pd/TiO2 catalysts that are able to reduce the formation of acid catalyzed products, e. g. ethers, for the hydrogenation of furfural. Transmission electron microscopy found a significant increase in polyvinyl alcohol (PVA) deposition at the metal‐support interface and temperature programmed reduction found a reduced uptake of hydrogen, compared to an established Pd/TiO2 preparation. We propose that the additional PVA hinders hydrogen spillover onto the TiO2 support and limits the formation of Brønsted acid sites, required to produce ethers. Elsewhere, the new preparation route was able to successfully anchor colloidal Pd to the TiO2 surface, without the need for acidification. This work demonstrates the potential for minimizing process steps as well as optimizing catalyst selectivity – both important objectives for sustainable chemistry. [ABSTRACT FROM AUTHOR]

The utilization of operando spectroscopy has allowed us to watch the dynamic nature of supported metal nanoparticles. However, the realization that subtle changes to environmental conditions affect the form of the catalyst necessitates that we assess the structure of the catalyst across the reactant/product gradient that exists across a fixed bed reactor. In this study, we have performed spatial profiling of a Pd/Al 2 O 3 catalyst during NH 3 oxidation, simultaneously collecting mass spectrometry and X-ray absorption spectroscopy data at discrete axial positions along the length of the catalyst bed. The spatial analysis has provided unique insights into the structure-activity relationships that govern selective NH 3 oxidation-(i) our data is consistent with the presence of PdN x after the spectroscopic signatures for bulk PdN x disappear and that there is a direct correlation to the presence of this structure and the selectivity toward N 2 ; (ii) at high temperatures, ≥400 °C, we propose that there are two simultaneous reaction pathways-the oxidation of NH 3 to NO x by PdO and the subsequent catalytic reduction of NO x by NH 3 to produce N 2 . The results in this study confirm the structural and catalytic diversity that exists during catalysis and the need for such an understanding if improvements to important emission control technologies, such as the selective catalytic oxidation of NH 3 , are to be made., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

We have made high surface area catalysts for the selective oxidation of methanol to formaldehyde. This is done in two ways - (i) by doping haematite with Al ions, to increase the surface area of the material, but which itself is unselective and (ii) by surface coating with Mo which induces high selectivity. Temperature programmed desorption (TPD) of methanol shows little difference in surface chemistry of the doped haematite from the undoped material, with the main products being CO 2 and CO, but shifted to somewhat higher desorption temperature. However, when Mo is dosed onto the haematite surface, the chemistry changes completely to show mainly the selective product, formaldehyde, with no CO 2 production, and this is little changed up to 10% Al loading. But at 15 wt% Al, the chemistry changes to indicate the presence of a strongly acidic function at the surface, with additional dimethyl ether and CO/CO 2 production characteristic of the presence of alumina. Structurally, X-ray diffraction (XRD) shows little change over the range 0-20% Al doping, except for some small lattice contraction, while the surface area increases from around 20 to 100 m 2 g -1 . Using X-ray absorption spectroscopy (XAS) it is clear that, at 5% loading, the Al is incorporated into the Fe 2 O 3 corundum lattice, which has the same structure as α-alumina. By 10% loading then it appears that the alumina starts to nano-crystallise within the haematite lattice into the γ form. At higher loadings, there is evidence of phase separation into separate Al-doped haematite and γ-alumina. If we add 1 monolayer equivalent of Mo to the surface there is already high selectivity to formaldehyde, but little change in structure, because that monolayer is isolated at the surface. However, when three monolayers equivalent of Mo is added, we then see aluminium molybdate type signatures in the XANES spectra at 5% Al loading and above. These appear to be in a sub-surface layer with Fe molybdate, which we interpret as due to Al substitution into ferric molybdate layers immediately beneath the topmost surface layer of molybdena. It seems like the separate γ-alumina phase is not covered by molybdena and is responsible for the appearance of the acid function products in the TPD.

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.

Carbon monoxide (CO) purification from syngas impurities is a highly energy and cost intensive process. Adsorption separation using metal-organic frameworks (MOFs) is being explored as an alternative technology for CO/nitrogen (N 2 ) and CO/carbon dioxide (CO 2 ) separation. Currently, MOFs' uptake and selectivity levels do not justify displacement of the current commercially available technologies. Herein, we have impregnated a leading MOF candidate for CO purification, i.e. M-MOF-74 (M = Co or Ni), with Cu + sites. Cu + allows strong π-complexation from the 3d electrons with CO, potentially enhancing the separation performance. We have optimised the Cu loading procedure and confirmed the presence of the Cu + sites using X-ray absorption fine structure analysis (XAFS). In situ XAFS and diffuse reflectance infrared Fourier Transform spectroscopy analyses have demonstrated Cu + -CO binding. The dynamic breakthrough measurements showed an improvement in CO/N 2 and CO/CO 2 separations upon Cu impregnation. This is because Cu sites do not block the MOF metal sites but rather increase the number of sites available for interactions with CO, and decrease the surface area/porosity available for adsorption of the lighter component., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)