Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In2O3/HZSM-5 Tandem CO2 Hydrogenation Catalyst.

Identifying the descriptors for the synergistic catalytic activity of bifunctional oxide-zeolite catalysts constitutes a formidable challenge in realizing the potential of tandem hydrogenation of CO2 to hydrocarbons (HC) for sustainable fuel production. Herein, we combined CH3OH synthesis from CO2 and H2 on In2O3 and methanol-to-hydrocarbons (MTH) conversion on HZSM-5 and discerned the descriptors by leveraging the distance-dependent reactivity of bifunctional In2O3 and HZSM-5 admixtures. We modulated the distance between redox sites of In2O3 and acid sites of HZSM-5 from milliscale (∼10 mm) to microscale (∼300 µm) and observed a 3-fold increase in space-time yield of HC and CH3OH (7.5 × 10-5 molC gcat-1 min-1 and 2.5 × 10-5 molC gcat-1 min-1, respectively), due to a 10-fold increased rate of CH3OH advection (1.43 and 0.143 s-1 at microscale and milliscale, respectively) from redox to acid sites. Intriguingly, despite the potential of a three-order-of-magnitude enhanced CH3OH transfer at a nanoscale distance (∼300 nm), the sole product formed was CH4. Our reactivity data combined with Raman, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) revealed the occurrence of solid-state-ion-exchange (SSIE) between acid sites and Inδ+ ions, likely forming In2O moieties, inhibiting C-C coupling and promoting CH4 formation through CH3OH hydrodeoxygenation (HDO). Density functional theory (DFT) calculations further revealed that CH3OH adsorption on the In2O moiety with preadsorbed and dissociated H2 forming an H-In-OH-In moiety is the likely reaction mechanism, with the kinetically relevant step appearing to be the hydrogenation of the methyl species. Overall, our study revealed that efficient CH3OH transfer and prevention of ion exchange are the key descriptors in achieving catalytic synergy in bifunctional In2O3/HZSM-5 systems.

Biological treatment of DMSO-containing wastewater from semiconductor industry under aerobic and methanogenic conditions.

This study evaluated biological treatment of dimethyl sulfoxide (DMSO)-containing wastewater from semiconductor industry under aerobic and anaerobic conditions. DMSO concentration as higher as 1.5 g/L did not inhibit DMSO degradation efficiency in aerobic membrane bioreactor (MBR), while specific DMSO degradation rate at different initial DMSO-to-biomass (S0/X0) ratios from batch tests seemed to follow the Haldane-type kinetics. According to the microbial community analysis, Proteobacteria decreased from 88.2% to 26% as influent DMSO concentration increased, while Bacteroidetes, Parcubacteria, Saccharibacteria increased. Within the Bacteroidetes class, Flavobacterium and Laribacter genus significantly increased from less than 0.05%-26.8% and 13.4%, respectively, which might both be related to the DMS degradation. Hyphomicrobium and Thiobacillus, known as aerobic DMSO and DMS degraders, instead, decreased at higher DMSO conditions. Under methanogenic conditions, batch results implied DMSO concentrations higher than 3 g/L could be inhibitory, while DMSO and COD removal achieved 100% and 93%, respectively, using a pilot-scale anaerobic fluidized bed membrane bioreactor (AFMBR) with influent DMSO below 1.5 g/L. Results of terminal restriction fragment length polymorphism (TRFLP) analysis targeting on mcrA functional gene revealed that Methanomethylovorans sp. was dominant in AFMBR after 54 days of operation, indicating its importance on degrading DMS and mathanethiol (MT).