XPS surface analysis of ceria-based materials: Experimental methods and considerations

X-ray photoelectron spectroscopy (XPS) analysis of cerium is ubiquitous amongst the catalytic and materials literature however errors in experimental procedure and data analysis are often easily proliferated. In this work we focus on the best practice for experimental construction when approaching the task of understanding chemical environments in cerium-based materials by XPS

Metal-Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al-SBA-15

Invited for this month′s cover is the group of Karen Wilson and Adam Lee at RMIT University. The image shows platinum nanoparticles and Brønsted acid sites working cooperatively to catalyse the efficient hydrodeoxygenation of phenolic lignin residues to produce sustainable biofuels. The Full Paper itself is available at 10.1002/cssc.202000764

Ethanol Steam Reforming for Hydrogen Production Over Hierarchical Macroporous Mesoporous SBA-15 Supported Nickel Nanoparticles

The influence of complementary macropores, present in hierarchical macroporous mesoporous SBA-15, on the performance of supported Ni nanoparticles for ethanol steam reforming has been investigated. The increased open nature of the architecture, afforded through the incorporation of the secondary macropore network, enables superior metal dispersion. This, in turn, enhances catalytic hydrogen production performance through the generation of a greater density of active sites

Support enhanced alpha-pinene isomerization over HPW/SBA-15

A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15

Platinum catalysed aerobic selective oxidation of cinnamaldehyde to cinnamic acid

Aerobic selective oxidation of allylic aldehydes offers an atom and energy efficient route to unsaturated carboxylic acids, however suitable heterogeneous catalysts offering high selectivity and productivity have to date proved elusive. Herein, we demonstrate the direct aerobic oxidation of cinnamaldehyde to cinnamic acid employing silica supported Pt nanoparticles under base-free, batch and continuous flow operation. Surface and bulk characterisation of four families of related Pt/silica catalysts by XRD, XPS, HRTEM, CO chemisorption and N_{2} porosimetry evidence surface PtO_{2} as the common active site for cinnamaldehyde oxidation, with a common turnover frequency of 49,000 ± 600 h^{-1}; competing cinnamaldehyde hydrogenolysis is favoured over metallic Pt. High area mesoporous (SBA-15 or KIT-6) and macroporous-mesoporous SBA-15 silicas confer significant rate and cinnamic acid yield enhancements versus low area fumed silica, due to superior platinum dispersion. High oxygen partial pressures and continuous flow operation stabilise PtO_{2} active sites against in-situ reduction and concomitant deactivation, further enhancing cinnamic acid productivity

Palladium-doped hierarchical ZSM-5 for catalytic selective oxidation of allylic and benzylic alcohols

Hierarchical zeolites have the potential to provide a breakthrough in transport limitation, which hinders pristine microporous zeolites and thus may broaden their range of applications. We have explored the use of Pd-doped hierarchical ZSM-5 zeolites for aerobic selective oxidation (selox) of cinnamyl alcohol and benzyl alcohol to their corresponding aldehydes. Hierarchical ZSM-5 with differing acidity (H-form and Na-form) were employed and compared with two microporous ZSM-5 equivalents. Characterization of the four catalysts by X-ray diffraction, nitrogen porosimetry, NH 3 temperature-programmed desorption, CO chemisorption, high-resolution scanning transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy allowed investigation of their porosity, acidity, as well as Pd active sites. The incorporation of complementary mesoporosity, within the hierarchical zeolites, enhances both active site dispersion and PdO active site generation. Likewise, alcohol conversion was also improved with the presence of secondary mesoporosity, while strong Brønsted acidity, present solely within the H-form systems, negatively impacted overall selectivity through undesirable self-etherification. Therefore, tuning support porosity and acidity alongside active site dispersion is paramount for optimal aldehyde production

Tunable Ag@SiO2 core-shell nanocomposites for broad spectrum antibacterial applications

Silica encapsulated silver nanoparticle core–shell nanocomposites of tunable dimensions were synthesised via a one-pot reverse microemulsion route to achieve controlled release of Ag+ ions for broad spectrum antibacterial application. Silver release rates and bactericidal efficacy against Gram-positive and Gram-negative bacteria, S. aureus and P. aeruginosa respectively, were inversely proportional to nanoparticle core diameter (3–8 nm) and silica shell (7–14 nm) thickness, and readily tuned through a facile hydrothermal etching protocol employing a PVP stabiliser to introduce mesoporosity

Hydrodeoxygenation of anisole over Pt/Al‐SBA‐15: metal‐acid synergy

Invited for this month′s cover is the group of Karen Wilson and Adam Lee at RMIT University. The image shows platinum nanoparticles and Brønsted acid sites working cooperatively to catalyse the efficient hydrodeoxygenation of phenolic lignin residues to produce sustainable biofuels. The Full Paper itself is available at 10.1002/cssc.202000764

Delaminated CoAl‐Layered Double Hydroxide@TiO₂ Heterojunction Nanocomposites for Photocatalytic Reduction of CO₂

Photocatalytic reduction offers an attractive route for CO_{2} utilization as a chemical feedstock for solar fuels production but remains challenging due to the poor efficiency, instability, and/or toxicity of current catalyst systems. Delaminated CoAl‐layered double hydroxide nanosheets (LDH‐DS) combined with TiO_{2} nanotubes (NTs) or nanoparticles (NPs) are promising nanocomposite photocatalysts for CO_{2} reduction. Heterojunction formation between visible light absorbing delaminated CoAl nanosheets and UV light absorbing TiO_{2} nanotubes greatly enhances interfacial contact between both high aspect ratio components relative to their bulk counterparts. The resulting synergic interaction confers a significant improvement in photoinduced charge carrier separation, and concomitant aqueous phase CO_{2} photocatalytic reduction, in the absence of a sacrificial hole acceptor. CO productivity for a 3 wt% LDH‐DS@TiO2‐NT nanocomposite of 4.57 µmol g_{cat}^{-1} h^{-1} exhibits a tenfold and fivefold increase over that obtained for individual TiO2 NT and delaminated CoAl‐LDH components respectively and is double that obtained for 3 wt% bulk‐LDH@TiO_{2}-NT and 3 wt% LDH‐DS@TiO2‐NP catalysts. Synthesis of delaminated LDH and metal oxide nanocomposites represents a cost‐effective strategy for aqueous phase CO_{2} reduction

Tailored mesoporous silica supports for Ni catalysed hydrogen production from ethanol steam reforming

Mesoporous silica supported Ni nanoparticles have been investigated for hydrogen production from ethanol steam reforming. Ethanol reforming is structure-sensitive over Ni, and also dependent on support mesostructure; three-dimensional KIT-6 possessing interconnected mesopores offers superior metal dispersion, steam reforming activity, and on-stream stability against deactivation compared with a two-dimensional SBA-15 support