CO2 hydrogenation selectivity shift over In-Co binary oxides catalysts: Catalytic mechanism and structure-property relationship

Li, Longtai; Yang, Bin; Gao, Biao; Wang, Yifu; Zhang, Lingxia; Ishihara, Tatsumi; Qi, Wei; Guo, Limin

doi:10.1016/s1872-2067(21)63870-6

Cited by 20 publications

(12 citation statements)

References 64 publications

(132 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This proves that the adsorption of CO is enhanced by nitrogen doping. Moreover, the peaks attributed to carbonates (CO 3 2– : 1308 and 1577 cm –1 ), carboxylates (HCOO – : 1378, 1425, 1580, and 1640 cm –1 ), and hydroxyls (OH – : 1223 cm –1 ) − are also observed, as shown in Figure C,D. For the N–In 2 O 3 catalyst, during the argon purging, the peaks of the adsorbed CO* and OH – intermediates are gradually weakening, while the peaks of the HCOO – intermediate first increase and then decrease.…”

Section: Resultsmentioning

confidence: 99%

Enhanced Surface Charge Localization Over Nitrogen-Doped In₂O₃ for CO₂ Hydrogenation to Methanol with Improved Stability

et al. 2023

View full text Add to dashboard Cite

Indium oxide (In 2 O 3 ) is active and promising for selective hydrogenation of CO 2 to methanol. However, it suffers from over-reduction at elevated temperatures, causing deactivation. Herein, a nitrogen-doped In 2 O 3 (N−In 2 O 3 ) catalyst was prepared using a plasma-intensified nitrogen-doping technology. It is confirmed that nitrogen doping is effective for the stabilization of In 2 O 3 . The doped nitrogen enhances the surface charge localization, which inhibits the over-reduction on the oxide surface and limits the generation of excessive surface oxygen vacancies. The doped nitrogen also serves as the active site, synergistically with surface oxygen vacancy, which leads to an enhanced dissociation of CO 2 to adsorbed CO* intermediates. The electron-rich nitrogen causes a strong adsorption of CO on N−In 2 O 3 and inhibits the formation of free CO. A significantly improved methanol selectivity with a higher turnover frequency (TOF) is thus achieved on N− In 2 O 3 , compared to the un-doped In 2 O 3 . For example, at 21,000 cm 3 h −1 g cat −1 , 300 °C, and 5 MPa, the TOF of N−In 2 O 3 reaches 37.0 h −1 with methanol selectivity of 75.1%, while the TOF of the un-doped In 2 O 3 is only 16.0 h −1 with methanol selectivity of 62.3%. Different from pristine In 2 O 3 , N−In 2 O 3 takes the CO hydrogenation route for CO 2 hydrogenation to methanol. This explains the reason why the N−In 2 O 3 catalyst possesses improved selectivity for CO 2 hydrogenation to methanol.

show abstract

Section: Resultsmentioning

confidence: 99%

Enhanced Surface Charge Localization Over Nitrogen-Doped In₂O₃ for CO₂ Hydrogenation to Methanol with Improved Stability

et al. 2023

View full text Add to dashboard Cite

show abstract

“…The interface structure of the Co 3 O 4 /ZnO catalyst has been investigated by Raman spectroscopy. The modes at 487 and 438 cm –1 correspond to ZnO, and the 708 cm –1 ( A 1 g ) and 528 cm –1 ( F 2 g ) signals indicate the presence of the Co 3 O 4 phase in the Co 3 O 4 /ZnO catalyst (Figure a). , More importantly, the Co 3 O 4 Raman peaks from Co 3 O 4 /ZnO are blue-shifted compared with that of pure Co 3 O 4 . The Co–O bond force constant ( k ) representing the Co–O bond strength can be calculated using Hooke’s law, , which is 372 and 344 N/m for Co 3 O 4 /ZnO and Co 3 O 4 , respectively.…”

Section: Resultsmentioning

confidence: 94%

Disentangling Local Interfacial Confinement and Remote Spillover Effects in Oxide–Oxide Interactions

Cheng

et al. 2023

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Supported oxides are widely used in many important catalytic reactions, in which the interaction between the oxide catalyst and oxide support is critical but still remains elusive. Here, we construct a chemically bonded oxide−oxide interface by chemical deposition of Co 3 O 4 onto ZnO powder (Co 3 O 4 /ZnO), in which complete reduction of Co 3 O 4 to Co 0 has been strongly impeded. It was revealed that the local interfacial confinement effect between Co oxide and the ZnO support helps to maintain a metastable CoO x state in CO 2 hydrogenation reaction, producing 93% CO. In contrast, a physically contacted oxide−oxide interface was formed by mechanically mixing Co 3 O 4 and ZnO powders (Co 3 O 4 −ZnO), in which reduction of Co 3 O 4 to Co 0 was significantly promoted, demonstrating a quick increase of CO 2 conversion to 45% and a high selectivity toward CH 4 (92%) in the CO 2 hydrogenation reaction. This interface effect is ascribed to unusual remote spillover of dissociated hydrogen species from ZnO nanoparticles to the neighboring Co oxide nanoparticles. This work clearly illustrates the equally important but opposite local and remote effects at the oxide−oxide interfaces. The distinct oxide− oxide interactions contribute to many diverse interface phenomena in oxide−oxide catalytic systems.

show abstract

“…Re cluster introduced a high coverage of CO species, including linearly bound to Re at the top (2025 cm -1 , COlin-Re), bridge bound to Re atoms (1867 cm -1 , CObri-Re), bridge bound between Re and TiO2 (1925 cm -1 , CObri-ReTi), CO-Re1 (2120 cm -1 ) aside from the relatively low coverage of formate. CH4 and gas phase CO were also observed by their characteristic vibrational modes at 3018 and 2170 cm -1 [39] . In contrast to Re1/TiO2 catalyst, where formates species predominated the surface, Re cluster was almost saturated by CO species besides a small quantity of formates.…”

Section: Size-dependent Active Sites and Reaction Mechanismmentioning

confidence: 98%

Size-dependent active site and its catalytic mechanism for CO2 hydrogenation reactivity and selectivity over Re/TiO2

Yang

Wang

Gao

et al. 2023

Preprint

View full text Add to dashboard Cite

The relationship of structure sensitive between metal size and CO2 hydrogenation performance are still unclear. Herein, using a unique set of well-defined TiO2-support rhenium (Re) catalysts and systematical characterizations, we clearly demonstrate the size-dependent active site and reaction mechanism is closely related to size effect. A wave-like size dependent activity of CO2 conversion is also identified. In the size range from single atom to 1.0 nm, reverse water gas shift (RWGS) reaction controls CO2 hydrogenation and its turn over frequency decrease with the size increasing. Whereas, over 1.0 nm cluster, CO2 methanation is the main reaction and exhibits a volcano-like size dependent performance. Mechanistic studies reveal the perimeter sites in single atom catalysts dictate RWGS reaction via formate pathways. In contrast, the active site in Re cluster is edge site, where CO2 reduce to CO via redox pathway and subsequently hydrogenate to methane over edge site. This discovery may deepen the mechanistic understanding of structure sensitive.

show abstract

CO2 hydrogenation selectivity shift over In-Co binary oxides catalysts: Catalytic mechanism and structure-property relationship

Cited by 20 publications

References 64 publications

Enhanced Surface Charge Localization Over Nitrogen-Doped In₂O₃ for CO₂ Hydrogenation to Methanol with Improved Stability

Enhanced Surface Charge Localization Over Nitrogen-Doped In₂O₃ for CO₂ Hydrogenation to Methanol with Improved Stability

Disentangling Local Interfacial Confinement and Remote Spillover Effects in Oxide–Oxide Interactions

Size-dependent active site and its catalytic mechanism for CO2 hydrogenation reactivity and selectivity over Re/TiO2

Contact Info

Product

Resources

About

CO2 hydrogenation selectivity shift over In-Co binary oxides catalysts: Catalytic mechanism and structure-property relationship

Cited by 20 publications

References 64 publications

Enhanced Surface Charge Localization Over Nitrogen-Doped In2O3 for CO2 Hydrogenation to Methanol with Improved Stability

Enhanced Surface Charge Localization Over Nitrogen-Doped In2O3 for CO2 Hydrogenation to Methanol with Improved Stability

Disentangling Local Interfacial Confinement and Remote Spillover Effects in Oxide–Oxide Interactions

Size-dependent active site and its catalytic mechanism for CO2 hydrogenation reactivity and selectivity over Re/TiO2

Contact Info

Product

Resources

About

Enhanced Surface Charge Localization Over Nitrogen-Doped In₂O₃ for CO₂ Hydrogenation to Methanol with Improved Stability

Enhanced Surface Charge Localization Over Nitrogen-Doped In₂O₃ for CO₂ Hydrogenation to Methanol with Improved Stability