Atomically Strained Metal Sites for Highly Efficient and Selective Photooxidation

Abstract

Strain engineering is an attractive strategy for improving the intrinsic catalytic performance of heterogeneous catalysts. Manipulating strain on the short-range atomic scale to the local structure of the catalytic sites is still challenging. Herein, we successfully achieved atomic strain modulation on ultrathin layered vanadium oxide nanoribbons by an ingenious intercalation chemistry method. When trace sodium cations were introduced between the V 2 O 5 layers (Na + -V 2 O 5 ), the V−O bonds were stretched by the atomically strained vanadium sites, redistributing the local charges. The Na + -V 2 O 5 demonstrated excellent photooxidation performance, which was approximately 12 and 14 times higher than that of pristine V 2 O 5 and VO 2 , respectively. Complementary spectroscopy analysis and theoretical calculations confirmed that the atomically strained Na + -V 2 O 5 had a high surficial charge density, improving the activation of oxygen molecules and contributing to the excellent photocatalytic property. This work provides a new approach for the rational design of strain-equipped catalysts for selective photooxidation reactions.

Oxygen Vacancy Engineering of Fe-Doped NiMoO4 for Electrocatalytic N2 Fixation to NH3

“…Besides, according the corresponding HRTEM pictures of different Fe-NiMoO 4 samples (Figure a,f,k), the fast Fourier transform (FFT) patterns can be obtained (Figure b,g,l). The corresponding strain distribution diagrams (Figure c–e,h–j and m–o) show that with the introduction of Fe, the lattice strain distribution becomes more pronounced. − This indicates that the strain change of NiMoO 4 samples is more noticeable with the increase of Fe content.…”

Aqueous Topological Synthesis of Au@semiconductor Core–Shell Nanocrystals with Morphology and Composition Engineering

“…Colloidal core–shell nanocrystals (C–S NCs), especially the noble metal@semiconductor (NMS) C–S NCs with plasmon-exciton coupling effect, are an essential class of materials due to their tunable optical and electrical properties. − NMS C–S NCs have kept the controllable localized surface plasmon resonance (LSPR) effect from the noble metal, the widely tunable absorption benefiting from various compositions, and the maximum degree of functional coupling corresponding to the most extensive contact areas. − In the past decades, many strategies have been utilized to synthesize NMS C–S NCs, such as vapor deposition, molecular beam epitaxy, and colloidal epitaxial growth. − Beyond this, it is desirable to assume a general strategy with not only flexible morphology and composition engineering but also hydrophilic surface chemistry.…”

Unveiling dual catalysis enhancement of a pyridinium-containing Zn(ii) coordination polymer in aerobic photooxidation of organic substrates and selective photoreduction of CO2

“…1–4 Among them, photooxidation of organic substrates and photoreduction of CO 2 have gained a lot of attention in the past decade, as these reactions not only provide a fundamental understanding of photocatalysis but also show promising practical applications. 5–11 For example, oxidative coupling of amines to imines, oxygenation of sulfides to sulfoxides, oxidation of alcohols to carbonyl compounds, and dehydrogenation of N-heterocycles are several basic reactions in organic synthesis, which are also of significant importance in the production of pharmaceuticals and fine chemicals. 12–16 Using light energy to drive these oxidation reactions is believed to be green, sustainable, and economical, especially with earth-abundant catalysts and molecular O 2 as an oxidant in air under mild conditions.…”