Single‐Atomic‐Site Platinum Steers Middle Hydroxyl Selective Oxidation on Amorphous/Crystalline Homojunction for Photoelectrochemical Glycerol Oxidation Coupled with Hydrogen Generation

Abstract

Photoelectrochemical (PEC) organic conversion is a promising approach to convert low‐cost organics to value‐added chemicals, which urgently needs the development of efficient and highly selective photoanodes. Here, a Pt single‐atom dispersed WO3 amorphous/crystalline homojunction for anodic glycerol oxidation reaction (GOR) coupled with cathodic hydrogen generation is reported. In the coupled photoelectrocatalytic system, the novel Pt‐SA/WOx photoanode reaches a photocurrent density of 2.85 mA cm−2 at 1.2 V versus RHE, with up to 297.3 mmol m−2 h−1 of glycerol conversion rate and 60.2% of dihydroxyacetone (DHA) selectivity, realizing green synthesis of high‐value chemicals. The experimental data and theoretical calculations reveal the regulated band structure, build‐in electric field, and surface charge density of Pt‐SA/WOx, which can improve the carrier lifetime, accelerate charge transfer, and reduce the energy barrier for the GOR process, thus boosting PEC activity and DHA selectivity. This work provides a feasible plan for designing atomic‐level engineering and constructing amorphous/crystalline homojunction on photoanodes for efficient PEC high‐value products from biomass.

Changing Benzoxazole Ring into Nonring Imine Linkages on Covalent Organic Frameworks with Tuning H2O2 Photosynthesis Performance

“…Two-dimensional layers easily become irregular stacking, just like the XRD observation of recycled BDOH-Tb- IM samples and other previously reported results (Figure e). ,, The FT-IR signals of BDOH-Tb- IM before and after undergoing the recycling test recorded a slight change, suggesting its stability during photocatalysis (Figure f). The FT-IR signals of CO seem to become more remarkable after long-time testing, probably owing to surface oxidation of the −OH group on BDOH-Tb- IM . , The crystalline and molecule structures of BDOH-Tb- IM maintained a certain degree of stability in 0.1 M KOH and 0.1 M HCl solutions, corroborated by their slightly changed FT-IR signals, XRD patterns, and surface area (Figure S6).…”

“…The FT-IR signals of C�O seem to become more remarkable after long-time testing, probably owing to surface oxidation of the −OH group on BDOH-Tb-IM. 33,34 The crystalline and molecule structures of BDOH-Tb-IM maintained a certain degree of stability in 0.1 M KOH and 0.1 M HCl solutions, corroborated by their slightly changed FT-IR signals, XRD patterns, and surface area (Figure S6). 29−31 When N 2 -bubbling water was replaced with N 2presaturated water, the H 2 O 2 production rate of BDOH-Tb-IM reached over 780 μmol•g −1 •h −1 , which was higher than 459 μmol•g −1 •h −1 .…”