H2 activation is fundamental in catalysis. Single-atom catalysts (SACs) can be highly selective hydrogenation catalysts due to their tunable geometric and electronic properties. In this work, H2 activation (adsorption, splitting, and diffusion) on the anatase TiO2-supported SAC has been modeled in detail. The stable configurations of 14 transition metals from 3d to 5d (Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, and Au) and Sn have been screened. We compared H and H2 adsorption and H2 heterolytic and homolytic splitting on SA/TiO2. H on the SAC in neutral, hydridic, and proton forms and the preferred H2 dissociation paths are revealed. We found that the metal adatoms strengthen the Brønsted acids via forming the SA-O bonds and promote the H adsorption on Ti sites via forming the Ti3+ sites. The electronic descriptor using the energy level of the frontier d orbital, referenced to vacuum, can predict the single H and H2 dissociative adsorption energies on the metal site. As the SA-Hδ- interaction is stronger than Ti-Hδ-, the activation barriers for heterolytic paths over SA-O sites are lower than over Ti-O sites. H2 adsorption is activated on Au, Ru, Rh, Pd, and Ir in a dihydrogen complex structure with an elongated H-H bond. Homolytic splitting over SA sites is favored thermodynamically and kinetically on Rh, Pd, Os, Ir, and Pt. In contrast, for the remaining SA/TiO2, H-H splitting at the SA-O is kinetically favored compared to the Ti-O sites, but the products are less thermodynamically favored.
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Fluorogenic Reaction Probes Defect Sites on Titanium Dioxide Nanoparticles
Titanium dioxide nanoparticles (TiO2 NPs) have traditionally been utilized as industrial catalysts, finding widespread application in various chemical processes due to their exceptional stability and minimal toxicity. However, quantitatively assessing the reactive sites on TiO2 NPs remains a challenge. In this study, we employed a fluorogenic reaction to probe the apparent reactivity of TiO2 NPs. By manipulating the number of defect sites through control of hydrolysis speed and annealing temperature, we determined that the Ti(Ⅲ) content is positively correlated with the reactivity of TiO2 NPs. Additionally, these Ti(Ⅲ) sites could be introduced by reducing commercial TiO2 NPs using NaBH4. Our findings suggest that fluorogenic oxidation of Amplex Red is an effective method for probing defect site densities on TiO2 NPs. Utilizing single-molecule fluorescence imaging, we demonstrated the ability to map defect site density within TiO2 nanowires. Achieving sub-nanoparticle spatial resolution, we observed significant intraparticle and interparticle variations in the defect site distribution, leading to substantial reactivity heterogeneity.
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- Award ID(s):
- 2247709
- PAR ID:
- 10507763
- Editor(s):
- Charlotte Liu
- Publisher / Repository:
- Wiley-VCH GmbH
- Date Published:
- Journal Name:
- ChemNanoMat
- ISSN:
- 2199-692X
- Subject(s) / Keyword(s):
- TiO2 catalysis defect sites fluorogenic probe super-resolution imaging
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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