Lu Jing, Zhu Bo, Sakaki Shigeyoshi
Hubei Key Laboratory of Advanced Textile Materials & Application, Hubei International Scientific and Technological Cooperation Base of Intelligent Textile Materials & Application, Wuhan Textile University Wuhan 430200 China.
Element Strategy Initiative for Catalysts and Batteries, Kyoto University Goryo-Ohara 1-30, Nishikyo-ku Kyoto 615-8245 Japan
RSC Adv. 2020 Sep 30;10(59):36090-36100. doi: 10.1039/d0ra05738j. eCollection 2020 Sep 28.
The reaction of O with a Ru@Pt core-shell particle consisting of a Ru core and a Pt shell was theoretically investigated in comparison with Pt. The O binding energy with Pt is larger than that with Ru@Pt, and O-O bond cleavage occurs more easily with a smaller activation barrier ( ) on Pt than on Ru@Pt. Protonation to the Pt surface followed by one-electron reduction leads to the formation of an H atom on the surface with considerable exothermicity. The H atom reacts with the adsorbed O molecule to afford an OOH species with a larger value on Pt than on Ru@Pt. An OOH species is also formed by protonation of the adsorbed O molecule, followed by one-electron reduction, with a large exothermicity in both Pt and Ru@Pt. O-OH bond cleavage occurs with a smaller on Pt than on Ru@Pt. The lower reactivity of Ru@Pt than that of Pt on the O-O and O-OH bond cleavages arises from the presence of lower energy in the d-valence band-top and d-band center in Ru@Pt than in Pt. The smaller for OOH formation on Ru@Pt than on Pt arises from weaker Ru@Pt-O and Ru@Pt-H bonds than the Pt-O and Pt-H bonds, respectively. The low-energy d-valence band-top is responsible for the weak Ru@Pt-O and Ru@Pt-OH bonds. Thus, the low-energy d-valence band-top and d-band center are important properties of the Ru@Pt particle.
与铂相比，从理论上研究了氧与由钌核和铂壳组成的钌@铂核壳颗粒的反应。氧与铂的结合能大于与钌@铂的结合能，并且在铂上比在钌@铂上更容易发生氧-氧键断裂，其活化能垒更小（ ）。质子化到铂表面后再进行单电子还原会导致表面形成具有相当大放热效应的氢原子。氢原子与吸附的氧分子反应，在铂上生成的OOH物种的值比在钌@铂上更大。吸附的氧分子质子化后再进行单电子还原也会形成OOH物种，在铂和钌@铂中都会有较大的放热效应。在铂上发生O-OH键断裂的 比在钌@铂上更小。钌@铂在氧-氧键和O-OH键断裂方面的反应活性低于铂，这是由于钌@铂的d价带顶和d带中心的能量比铂中的低。钌@铂上形成OOH的 比铂上小，分别是因为钌@铂-O键和钌@铂-H键比铂-O键和铂-H键弱。低能量的d价带顶导致了钌@铂-O键和钌@铂-OH键较弱。因此，低能量的d价带顶和d带中心是钌@铂颗粒的重要性质。
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