Efficient in situ deposition of metallic cocatalyst, like zero‐valent platinum (Pt), on organic photovoltaic catalysts (OPCs) is the prerequisite for their high catalytic activities. Here we develop the OPC (Y6CO), by introducing carbonyl in the core, which is available to σ‐π coordinate with transition metals, due to the high‐energy empty π* orbital of carbonyl. Y6CO exhibits a stronger capability to anchor Pt species and reduce them to metallic state, resulting in more Pt0 deposition, relative to the control OPC without the central σ‐π anchor. Single‐component and heterojunction nanoparticles (NPs) employing Y6CO show enhanced average hydrogen evolution rates of 230.98 and 323.22 mmol h−1 g[OPC]−1, respectively, under AM 1.5G, 100 mW cm−2 for 10 h, and heterojunction NPs yield the external quantum efficiencies of ca. 10 % in 500–800 nm. This work demonstrates that σ‐π anchoring is one efficient strategy for integrating metallic cocatalyst and OPC for high‐performance photocatalysis.
The preparation of high value-added boronic acids from cheap and plentiful carboxylic acids is desirable. To date, the decarboxylative borylation of carboxylic acids is generally realized through the extra step synthesized redox-active ester intermediate or in situ generated carboxylic acid covalent derivatives above 150 °C reaction temperature. Here, we report a direct decarboxylative borylation method of carboxylic acids enabled by visible-light catalysis and that does not require any extra stoichiometric additives or synthesis steps. This operationally simple process produces CO2 and proceeds under mild reaction conditions, in terms of high step economy and good functional group compatibility. A guanidine-based biomimetic active decarboxylative mechanism is proposed and rationalized by mechanistic studies. The methodology reported herein should see broad application extending beyond borylation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.