One-Pot Pyrolysis to N-Doped Graphene with High-Density Pt Single Atomic Sites as Heterogeneous Catalyst for Alkene Hydrosilylation

Abstract

Development of noble-metal single atomic site catalysts with high metal loading is highly required for many important chemical reactions but proves to be very challenging. Herein, we report a Na 2 CO 3 salt-assisted one-pot pyrolysis strategy from EDTA−Pt complex to N-doped graphene with isolated Pt single atomic sites (Pt-ISA/NG) with Pt loading up to 5.3 wt %. The X-ray absorption fine structure analysis and spherical aberration-correction electron microscopy demonstrate an atomic dispersion of single Pt species on graphene support and stabilized by nitrogen in Pt−N 4 structure. The Pt-ISA/NG catalyst exhibits high catalytic activity and reusability for anti-Markovnikov hydrosilylation of various terminal alkenes with industrially relevant tertiary silanes under mild conditions. In hydrosilylation of 1-octene, the Pt-ISA/NG catalyst delivers an overall turnover frequency of 180 h −1 , which is a 4-fold enhancement compared with commercial Pt/C.

Alkene Hydrosilylation on Oxide‐Supported Pt‐Ligand Single‐Site Catalysts

“…A non‐supported (homogeneous) version of Pt‐DTPZ was not tested due to poor solubility in toluene. Average TOF values calculated by dividing TON per Pt by reaction time (5.4 s −1 at 60 °C, Table , entry 6) are significantly higher than previously reported values on other Pt SSCs, Pt δ+ /TiO 2 (<0.21 s −1 at 90 °C) and Pt/graphene (0.5 s −1 at 60 °C) at the same or even higher temperature, showing the superiority of our Pt‐DPTZ system. We note that metallic Pt NP are almost catalytically inactive when supported on MgO (entry 3).…”

Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion

“…The studied hard templates include SiO 2 nanospheres, branched SiO 2 nanoaggregates, ordered mesoporous SiO 2 , and MgO . The soft templates involved Na 2 CO 3 , KCl, hydrogels, and a self‐assembled FeCl 3 layer . For instance, Wan et al reported the synthesis of atomically dispersed FeN 4 on concave‐shaped octahedral carbon cages from SiO 2 coated ZIF‐8 precursors .…”

Single Au Atoms Anchored on Amino‐Group‐Enriched Graphitic Carbon Nitride for Photocatalytic CO2 Reduction

“…in 1995, the synthetic methodology and catalytic applications of single‐atom catalysts (SACs) have attracted worldwide attention. SACs have been shown to have high atom‐utilization efficiency as well as remarkable catalytic activity and selectivity . For example, various kinds of SACs have been prepared and investigated for silane oxidation, hydrogen evolution reaction, and alkene hydrosilylation .…”