{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"omics_type":["Unknown"],"volume":["12(13)"],"submitter":["Mahnaz F"],"pubmed_abstract":["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 CO<sub>2</sub> to hydrocarbons (HC) for sustainable fuel production. Herein, we combined CH<sub>3</sub>OH synthesis from CO<sub>2</sub> and H<sub>2</sub> on In<sub>2</sub>O<sub>3</sub> and methanol-to-hydrocarbons (MTH) conversion on HZSM-5 and discerned the descriptors by leveraging the distance-dependent reactivity of bifunctional In<sub>2</sub>O<sub>3</sub> and HZSM-5 admixtures. We modulated the distance between redox sites of In<sub>2</sub>O<sub>3</sub> 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 CH<sub>3</sub>OH (7.5 × 10<sup>-5</sup> mol<sub>C</sub> g<sub>cat</sub><sup>-1</sup> min<sup>-1</sup> and 2.5 × 10<sup>-5</sup> mol<sub>C</sub> g<sub>cat</sub><sup>-1</sup> min<sup>-1</sup>, respectively), due to a 10-fold increased rate of CH<sub>3</sub>OH advection (1.43 and 0.143 s<sup>-1</sup> at microscale and milliscale, respectively) from redox to acid sites. Intriguingly, despite the potential of a three-order-of-magnitude enhanced CH<sub>3</sub>OH transfer at a nanoscale distance (∼300 nm), the sole product formed was CH<sub>4</sub>. 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 In<sup>δ+</sup> ions, likely forming In<sub>2</sub>O moieties, inhibiting C-C coupling and promoting CH<sub>4</sub> formation through CH<sub>3</sub>OH hydrodeoxygenation (HDO). Density functional theory (DFT) calculations further revealed that CH<sub>3</sub>OH adsorption on the In<sub>2</sub>O moiety with preadsorbed and dissociated H<sub>2</sub> 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 CH<sub>3</sub>OH transfer and prevention of ion exchange are the key descriptors in achieving catalytic synergy in bifunctional In<sub>2</sub>O<sub>3</sub>/HZSM-5 systems."],"journal":["ACS sustainable chemistry & engineering"],"pagination":["5197-5210"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10988559"],"repository":["biostudies-literature"],"pubmed_title":["Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In<sub>2</sub>O<sub>3</sub>/HZSM-5 Tandem CO<sub>2</sub> Hydrogenation Catalyst."],"pmcid":["PMC10988559"],"pubmed_authors":["Lin YT","Mahnaz F","Vito J","Mangalindan JR","Shetty M","Akbulut M","Dharmalingam BC","Varghese JJ"],"additional_accession":[]},"is_claimable":false,"name":"Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In<sub>2</sub>O<sub>3</sub>/HZSM-5 Tandem CO<sub>2</sub> Hydrogenation Catalyst.","description":"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 CO<sub>2</sub> to hydrocarbons (HC) for sustainable fuel production. Herein, we combined CH<sub>3</sub>OH synthesis from CO<sub>2</sub> and H<sub>2</sub> on In<sub>2</sub>O<sub>3</sub> and methanol-to-hydrocarbons (MTH) conversion on HZSM-5 and discerned the descriptors by leveraging the distance-dependent reactivity of bifunctional In<sub>2</sub>O<sub>3</sub> and HZSM-5 admixtures. We modulated the distance between redox sites of In<sub>2</sub>O<sub>3</sub> 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 CH<sub>3</sub>OH (7.5 × 10<sup>-5</sup> mol<sub>C</sub> g<sub>cat</sub><sup>-1</sup> min<sup>-1</sup> and 2.5 × 10<sup>-5</sup> mol<sub>C</sub> g<sub>cat</sub><sup>-1</sup> min<sup>-1</sup>, respectively), due to a 10-fold increased rate of CH<sub>3</sub>OH advection (1.43 and 0.143 s<sup>-1</sup> at microscale and milliscale, respectively) from redox to acid sites. Intriguingly, despite the potential of a three-order-of-magnitude enhanced CH<sub>3</sub>OH transfer at a nanoscale distance (∼300 nm), the sole product formed was CH<sub>4</sub>. 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 In<sup>δ+</sup> ions, likely forming In<sub>2</sub>O moieties, inhibiting C-C coupling and promoting CH<sub>4</sub> formation through CH<sub>3</sub>OH hydrodeoxygenation (HDO). Density functional theory (DFT) calculations further revealed that CH<sub>3</sub>OH adsorption on the In<sub>2</sub>O moiety with preadsorbed and dissociated H<sub>2</sub> 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 CH<sub>3</sub>OH transfer and prevention of ion exchange are the key descriptors in achieving catalytic synergy in bifunctional In<sub>2</sub>O<sub>3</sub>/HZSM-5 systems.","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Apr","modification":"2024-12-04T06:50:19.825Z","creation":"2024-12-04T06:50:19.825Z"},"accession":"S-EPMC10988559","cross_references":{"pubmed":["38577585"],"doi":["10.1021/acssuschemeng.3c08250"]}}