Bifunctional hydroformylation on heterogeneous Rh-WOx pair site catalysts.

Metal-catalysed reactions are often hypothesized to proceed on bifunctional active sites, whereby colocalized reactive species facilitate distinct elementary steps in a catalytic cycle1-8. Bifunctional active sites have been established on homogeneous binuclear organometallic catalysts9-11. Empirical evidence exists for bifunctional active sites on supported metal catalysts, for example, at metal-oxide support interfaces2,6,7,12. However, elucidating bifunctional reaction mechanisms on supported metal catalysts is challenging due to the distribution of potential active-site structures, their dynamic reconstruction and required non-mean-field kinetic descriptions7,12,13. We overcome these limitations by synthesizing supported, atomically dispersed rhodium-tungsten oxide (Rh-WOx) pair site catalysts. The relative simplicity of the pair site structure and sufficient description by mean-field modelling enable correlation of the experimental kinetics with first principles-based microkinetic simulations. The Rh-WOx pair sites catalyse ethylene hydroformylation through a bifunctional mechanism involving Rh-assisted WOx reduction, transfer of ethylene from WOx to Rh and H2 dissociation at the Rh-WOx interface. The pair sites exhibited >95% selectivity at a product formation rate of 0.1 gpropanal cm-3 h-1 in gas-phase ethylene hydroformylation. Our results demonstrate that oxide-supported pair sites can enable bifunctional reaction mechanisms with high activity and selectivity for reactions that are performed in industry using homogeneous catalysts.

Catalytic Approaches to Tackle Mixed Plastic Waste Challenges: A Review.

Plastics are widely used materials in our daily lives and various industries due to their affordability and versatility. The massive production of plastic waste, however, has recently emerged as a pressing environmental concern across all media. To address this, emerging technologies are being explored for the sustainable valorization of postconsumer plastic wastes including thermochemical, physical, and catalytic processes aimed at transforming them into higher value-added products. However, the chemical recycling of mixed plastic wastes poses a formidable challenge due to the diverse array of monomers and catalyst systems involved, each employing distinct mechanisms. Complicating matters further is that contaminants reduce catalytic efficacy, requiring rigorous and labor-intensive separation and purification processes to extract individual plastic streams from practical plastic waste mixtures. Consequently, the majority of such mixtures often end up in incineration and landfills, perpetuating environmental and societal challenges, such as leachate, carbon dioxide emissions, and other air pollutants. This review will introduce current technical developments available for recycling practical plastic waste mixtures through catalytic processes. The current challenges in process performance, low selectivity of the desired products, and catalyst deactivation from the catalysis of plastic waste mixtures are also discussed. Promising approaches to overcome the problems are suggested in future research directions.

Structural evolution of atomically dispersed Pt catalysts dictates reactivity.

The use of oxide-supported isolated Pt-group metal atoms as catalytic active sites is of interest due to their unique reactivity and efficient metal utilization. However, relationships between the structure of these active sites, their dynamic response to environments and catalytic functionality have proved difficult to experimentally establish. Here, sinter-resistant catalysts where Pt was deposited uniformly as isolated atoms in well-defined locations on anatase TiO2 nanoparticle supports were used to develop such relationships. Through a combination of in situ atomic-resolution microscopy- and spectroscopy-based characterization supported by first-principles calculations it was demonstrated that isolated Pt species can adopt a range of local coordination environments and oxidation states, which evolve in response to varied environmental conditions. The variation in local coordination showed a strong influence on the chemical reactivity and could be exploited to control the catalytic performance.

Reverse Water-Gas Shift on Interfacial Sites Formed by Deposition of Oxidized Molybdenum Moieties onto Gold Nanoparticles.

We show that MoO(x)-promoted Au/SiO2 catalysts are active for reverse water-gas shift (RWGS) at 573 K. Results from reactivity measurements, CO FTIR studies, Raman spectroscopy, and X-ray absorption spectroscopy (XAS) indicate that the deposition of Mo onto Au nanoparticles occurs preferentially on under-coordinated Au sites, forming Au/MoO(x) interfacial sites active for reverse water-gas shift (RWGS). Au and AuMo sites are quantified from FTIR spectra of adsorbed CO collected at subambient temperatures (e.g., 150-270 K). Bands at 2111 and 2122 cm(-1) are attributed to CO adsorbed on under-coordinated Au(0) and Au(δ+) species, respectively. Clausius-Clapeyron analysis of FTIR data yields a heat of CO adsorption (ΔH(ads)) of -31 kJ mol(-1) for Au(0) and -64 kJ mol(-1) for Au(δ+) at 33% surface coverage. Correlations of RWGS reactivity with changes in FTIR spectra for samples containing different amounts of Mo indicate that interfacial sites are an order of magnitude more active than Au sites for RWGS. Raman spectra of Mo/SiO2 show a feature at 975 cm(-1), attributed to a dioxo (O═)2Mo(-O-Si)2 species not observed in spectra of AuMo/SiO2 catalysts, indicating preferential deposition of Mo on Au. XAS results indicate that Mo is in a +6 oxidation state, and therefore Au and Mo exist as a metal-metal oxide combination. Catalyst calcination increases the quantity of under-coordinated Au sites, increasing RWGS activity. This strategy for catalyst synthesis and characterization enables quantification of Au active sites and interfacial sites, and this approach may be extended to describe reactivity changes observed in other reactions on supported gold catalysts.

Investigating the impact of TiO2 crystalline phases on catalytic properties of Ru/TiO2 for hydrogenolysis of polyethylene plastic waste.

A series of TiO2-supported Ru catalysts with different TiO2 crystalline phases was synthesized and employed for the hydrogenolysis of polyethylene (PE). CO chemisorption, high-angle annular dark-field-scanning transmission electron microscopy, temperature-programmed reduction, and CO-Fourier transform infrared spectroscopy suggested that the degree of strong metal-support interactions (SMSIs) varied depending on the type of the TiO2 phase and the reduction temperature, eventually influencing the catalysis of PE hydrogenolysis. Among the synthesized catalysts, Ru/TiO2 with the rutile phase (Ru/TiO2-R) exhibited the highest catalytic activity after high-temperature reduction at 500 °C, indicating that a certain degree of SMSI is necessary for ensuring high activity in PE hydrogenolysis. Ru/TiO2-R could be successfully employed for the hydrogenolysis of post-consumer plastic wastes such as LDPE bottles to produce valuable chemicals (liquid fuel and wax) in high yields of 74.7%. This work demonstrates the possibility of harnessing the SMSIs in the design and synthesis of active catalysts for PE hydrogenolysis.

Fabrication of copper nanoparticles in a thick polyimide film cured by rapid thermal annealing.

We investigated the imidization of a polyimide (PI) and the formation of Cu nanoparticles in a PI film by curinga precursor of PI (polyamic acid (PAA) dissolved in n-methyl-2-pyrrolidinone) in a reducing atmosphere in the rapid thermal annealing (RTA) system. A Cu film was deposited onto the SiO2/Si substrate, and the PAA was spin-coated onto the Cu film. After the PAA reacted with the Cu film, soft-baking was performed to evaporate the solvent. Finally, the PAA was imidized to PI at 450 degrees C by curing in a reducing atmosphere with the RTA. Fourier transform infrared spectroscopy showed that the PAA was successfully imidized by the RTA. X-ray diffraction patterns revealed that Cu nanoparticles formed by RTA curing at 450 degrees C for 5 minutes in a reducing atmosphere, and transmission electron microscopy showed that Cu nanoparticles about 6.5 nm in size were uniformly dispersed in the PI film. Curing by RTA is an attractive method because it takes only a few minutes.

Plasmon-enhanced photoelectrochemical water splitting with size-controllable gold nanodot arrays.

Size-controllable Au nanodot arrays (50, 63, and 83 nm dot size) with a narrow size distribution (± 5%) were prepared by a direct contact printing method on an indium tin oxide (ITO) substrate. Titania was added to the Au nanodots using TiO(2) sols of 2-3 nm in size. This created a precisely controlled Au nanodot with 110 nm of TiO(2) overcoats. Using these precisely controlled nanodot arrays, the effects of Au nanodot size and TiO(2) overcoats were investigated for photoelectrochemical water splitting using a three-electrode system with a fiber-optic visible light source. From UV-vis measurement, the localized surface plasmon resonance (LSPR) peak energy (ELSPR) increased and the LSPR line width (Γ) decreased with decreasing Au nanodot size. The generated plasmonic enhancement for the photoelectrochemical water splitting reaction increased with decreasing Au particle size. The measured plasmonic enhancement for light on/off experiments was 25 times for the 50 nm Au size and 10 times for the 83 nm Au nanodot size. The activity of each catalyst increased by a factor of 6 when TiO2 was added to the Au nanodots for all the samples. The activity of the catalyst was proportional to the quality factor (defined as Q = E(LSPR)/Γ) of the plasmonic metal nanostructure. The enhanced water splitting performance with the decreased Au nanodot size is probably due to more generated charge carriers (electron/hole pair) by local field enhancement as the quality factor increases.