Controlling CO<sub>2</sub> hydrogenation selectivity by Rh-based catalysts with different crystalline phases of TiO<sub>2</sub>

Cao, Fenghai; Gong, Nana; Ma, Zixuan; Wang, Xiaoxing; Tan, Min‐Yu; Wu, Yingquan; Tan, Yisheng

doi:10.1039/d2cc00472k

Cited by 16 publications

(15 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Alternatively, the hydrogenation of CO 2 over titania‐supported small Rh clusters (2 wt %) yields 72.7 % of CH 4 , while CO was obtained as major product (73 %) when using small Fe clusters (2.5 wt %) [37] . A pronounced preference for methane was also established for smaller Rh/TiO 2 systems [38] (1 wt %) as well as Ir/TiO 2 catalytic systems [39] …”

Section: Resultsmentioning

confidence: 97%

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

et al. 2022

View full text Add to dashboard Cite

The rapidly growing interest for new heterogeneous catalytic systems providing high atomic efficiency along with high stability and reactivity triggered an impressive progress in the field of single‐atom catalysis. Nevertheless, unravelling the factors governing the interaction strength between the support and the adsorbed metal atoms remains a major challenge. Based on periodic density functional theory (DFT) calculations, this paper provides insight into the adsorption of single late transition metals on a defect‐free anatase surface. The obtained adsorption energies fluctuate, with the exception of Pd, between −3.11 and −3.80 eV and are indicative of a strong interaction. Depending on the considered transition metal, we could attribute the strength of this interaction with the support to i) an electron transfer towards anatase (Ru, Rh, Ni), ii) s‐d orbital hybridisation effects (Pt), or iii) a synergistic effect between both factors (Fe, Co, Os, Ir). The driving forces behind the adsorption were also found to be strongly related to Klechkowsky's rule for orbital filling. In contrast, the deviating behaviour of Pd is most likely associated with the lower dissociation enthalpy of the Pd−O bond. Additionally, the reactivity of these systems was evaluated using the Fermi weighted density of states approach. The resulting softness values can be clearly related to the electron configuration of the catalytic systems as well as with the net charge on the transition metal. Finally, these indices were used to construct a model that predicts the adsorption strength of CO on these anatase‐supported d‐metal atoms. The values obtained from this regression model show, within a 95 % probability interval, a correlation of 84 % with the explicitly calculated CO adsorption energies.

show abstract

Section: Resultsmentioning

confidence: 97%

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The facets/internal structure of crystalline photocatalysts provide the active planes/sites in the catalytic reaction, and the atomic coordination profiles of different crystals parameters (including facets, sizes, and crystallinity) exhibit unique electronic and optical properties, [260,261] so their photocatalytic performance is heavily dependent on the structure of the crystals themselves. [175] For example, for TiO 2 , the photocatalytic activity of anatase is superior to that of rutile and slate, [262,263] which is attributed to the active facets exposed by the different crystal types. Among them, the highenergy facets {001} are usually more suitable for solar energy conversion [264,265] than the thermodynamically stable {101}, so increasing the exposure of {001} facets can significantly improve the photoactivity of anatase TiO 2 .…”

Section: Crystals Engineeringmentioning

confidence: 99%

Trace to the Source: Self‐Tuning of MOF Photocatalysts

Zhou

Zhang

Xiao

et al. 2023

Advanced Energy Materials

View full text Add to dashboard Cite

Benefitting from ultra‐high porosity, large specific surface area (SSA), and rich active sites, metal–organic frameworks (MOFs) have emerged as a star material in energy and environment related applications, especially in photocatalysis. In comparison with conventional photocatalysts, MOFs can be customized in terms of electronic structure, photo‐responsiveness, and morphological dimensions by rational design, which means that MOFs eliminate the need for other species to achieve enhanced photocatalytic performance, such as metals, compounds, and polymers, which may introduce extra costs, be time‐consuming, be multi‐phase, or have an unclear mechanism. Most previous review works related to MOF photocatalysis have mixed self‐tuning and assisted‐tuning, which often gives an incomplete understanding. In this work, the self‐tunning of MOFs by analyzing component (as clusters, ligands, and inclusions), defect (defect engineering, as linkers, clusters, and oxygen vacancies (OVs), and crystal (as facets, dimensions, and amorphization) is summarized. Then, outstanding examples of these strategies applied to water redox, CO2/N2 reduction, organic conversion, and environmental treatment are discussed. Finally, the opportunities and challenges faced in the self‐tuning of MOFs are analyzed from different perspectives. This paper is a comprehensive and systematic review on the self‐tuning of MOFs to enhance photocatalytic activity.

show abstract

“…It should be noted that the hydrogenation reactions of CO 2 are exothermic, while the RWGS reaction is endothermic. 8 The thermodynamics properties determine that lower reaction temperatures and higher pressures are more favorable for CH 3 OH synthesis. 9 However, under such reaction conditions, the conventional Cu-based catalysts show poor catalytic activity for the hydrogenation of CO 2 to CH 3 OH due to high reaction energy barriers, RWGS reaction, and the easy sintering of copper particles.…”

mentioning

confidence: 99%

Surface conversion of CuO–ZnO to ZIF-8 to enhance CO₂adsorption for CO₂hydrogenation to methanol

et al. 2023

View full text Add to dashboard Cite

show abstract

Controlling CO₂ hydrogenation selectivity by Rh-based catalysts with different crystalline phases of TiO₂

Abstract: A series of Rh-based catalysts of various crystalline phases (P25, anatase, and rutile) were prepared via the incipient-wetness impregnation method. It was found that these catalysts had different metal-support interactions....

Cited by 16 publications

References 31 publications

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

Trace to the Source: Self‐Tuning of MOF Photocatalysts

Surface conversion of CuO–ZnO to ZIF-8 to enhance CO₂adsorption for CO₂hydrogenation to methanol

Contact Info

Product

Resources

About

Controlling CO2 hydrogenation selectivity by Rh-based catalysts with different crystalline phases of TiO2

Abstract: A series of Rh-based catalysts of various crystalline phases (P25, anatase, and rutile) were prepared via the incipient-wetness impregnation method. It was found that these catalysts had different metal-support interactions....

Cited by 16 publications

References 31 publications

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

Trace to the Source: Self‐Tuning of MOF Photocatalysts

Surface conversion of CuO–ZnO to ZIF-8 to enhance CO2adsorption for CO2hydrogenation to methanol

Contact Info

Product

Resources

About

Controlling CO₂ hydrogenation selectivity by Rh-based catalysts with different crystalline phases of TiO₂

Surface conversion of CuO–ZnO to ZIF-8 to enhance CO₂adsorption for CO₂hydrogenation to methanol