Enhanced Methanol Oxidation in Acid Media on Pt/S, P Co‐doped Graphene with 3D Porous Network Structure Engineering

Abstract

A sulfur and phosphorous co-doped three-dimensional graphene (3D-SPG)-supported Pt nanoparticle (Pt/3D-SPG) catalyst with a unique 3D porous network structure was synthesized and employed as an efficient, environmentally friendly and robust catalyst for the methanol oxidation reaction (MOR). The unique 3D porous network structure of 3D-SPG is in favor of uniformly supporting Pt nanoparticles with an average size of 2.09 nm as well as enhancement of the mass transport of reactants and products. Hence, the Pt/3D-SPG catalyst shows improved stability, an electrochemical surface area over 15.5 and 30.8 % larger, and MOR performance of 1.6 and 2.2 times higher than S and P co-doped and P-doped graphenesupported Pt nanoparticle (Pt/SPG and Pt/PG) catalysts, respectively. The enhanced CO tolerance of the Pt/3D-SPG catalyst may result from the 3D porous network structure, which was not only favorable to release CO efficiently from the metallic Pt surface, but also could concentrate many more hydroxyl groups for enhancing CO ads oxidation. The Pt/3D-SPG catalyst offer a unique strategy for designing and preparing 3D graphenebased catalysts, taking into account of the advantages of doping with different heteroatoms.

3D Graphene Materials: From Understanding to Design and Synthesis Control

“…By far, 3D graphene materials have played vital roles as conductive supports for metal nanoparticles, metal oxide nanoparticles, polymers and enzymes in photocatalytic reactions, − electrocatalytic water splitting, ,, fuel cells (for ORR and oxidation of organics like methanol, benzyl alcohol, etc. ), − metal-air batteries (for ORR and OER), − supercapacitors, ,,, metal-ion batteries, ,− chemical sensors, ,, flexible electronics, ,, and water disinfection …”

N-Doping Holey Graphene TiO2–Pt Composite as Efficient Electrocatalyst for Methanol Oxidation

“…Nevertheless, the N-doping does not solve the π–π stacking between graphene layers that lead to the aggregation and active point shielding of the loading catalyst, which would restrict the application of graphene as catalyst support. Various strategies have been put forward to solve this problem; for example, 3D graphene , has been constructed to reduce the π–π stacking between graphene layers.…”

Carbon‐Free Nanocoral‐Structured Platinum Electrocatalyst for Enhanced Methanol Oxidation Reaction Activity with Superior Poison Tolerance

“…According to Table , the developed ncs‐Pt catalyst exhibits superior poison tolerance ( j f /j b =5.62) towards CO intermediates compared to the commercial Pt/C ( j f /j b =2.89) catalyst in the same environment. Therefore, the superior poison tolerance might be occurred due to two reasons i) presence of defect rich ncs‐Pt surface which leads easy oxidation of CO species and ii) highly negative onset potential (−0.59 V) which suggests that easier removal of CO species . Since the Pt‐based catalysts are very sensitive to oxidize the carbonaceous species; therefore it also oxidizes the carbonaceous species effectively resulting in a higher poison tolerance ratio …”

“…Therefore, the superior poison tolerance might be occurred due to two reasons i) presence of defect rich ncs-Pt surface which leads easy oxidation of CO species and ii) highly negative onset potential (À 0.59 V) which suggests that easier removal of CO species. [49][50][51][52][53] Since the Pt-based catalysts are very sensitive to oxidize the carbonaceous species; therefore it also oxidizes the carbonaceous species effectively resulting in a higher poison tolerance ratio. [54] In DMFC, the loading of precious metals is a crucial matter of concern.…”