Highly Loaded Independent Pt⁰ Atoms on Graphdiyne for pH‐General Methanol Oxidation Reaction

Abstract

The emergence of platinum-based catalysts promotes efficient methanol oxidation reactions (MOR). However, the defects of such noble metal catalysts are high cost, easy poisoning, and limited commercial applications. The efficient utilization of a low-cost, anti-poisoning catalyst has been expected. Here, it is skillfully used N-doped graphdiyne (NGDY) to prepare a zero-valent platinum atomic catalyst (Pt/NGDY), which shows excellent activity, high pH adaptability, and high CO tolerance for MOR. The Pt/NGDY electrocatalysts for MOR with specific activity 154.2 mA cm −2 (1449.3 mA mg Pt −1 ), 29 mA cm −2 (296 mA mg Pt −1 ) and 22 mA cm −2 (110 mA mg Pt −1 ) in alkaline, acid, and neutral solutions. The specific activity of Pt/NGDY is 9 times larger than Pt/C in alkaline solution. Density functional theory (DFT) calculations confirm that the incorporation of electronegativity nitrogen atoms can increase the high coverage of Pt to achieve a unique atomic state, in which the shared contributions of different Pt sites reach the balance between the electroactivity and the stability to guarantee the higher performance of MOR and durability with superior anti-poisoning effect.

Toward Electrocatalytic Methanol Oxidation Reaction: Longstanding Debates and Emerging Catalysts

“…[144] Recently, GDY has also been used in the MOR catalyst system. [145,146] Li and coworkers anchored Pt 4.4 Cu NPs into the GDY nanochannel as illustrated in Figure 9c. [145] The superior protophilic ability of GDY favors the proton migration during MOR which not only reduces the energy barriers in each reaction step but also leaves more active sites for the reaction proceeding (Figure 9d).…”

Principal strategies for designing graphdiyne-based catalyst toward green hydrogen production from water electrolysis

“…And the triangular cavity within GDY structure serves optimized sites for the fixation of the individual atom. Since 2018, a series of vanguard works by Prof. Yuliang Li's group forcefully substantiated that it is an effective strategy to construct GDY-based atomic catalyst, not only for efficient hydrogen production via water electrolysis [46][47][48][49][50], but various applications including electrochemical ammonia synthesis [49,51], CO 2 reduction [52] and methanol oxidation [53]. And combined theoretical and experimental results continuously unveiled new effects and properties of those individual active sites designed by GDY fixation.…”

Low-Pt Octahedral PtCuCo Nanoalloys: “One Stone, Four Birds” for Oxygen Reduction and Methanol Oxidation Reactions

“…Pt alloying with earth-abundant 3d transition metals (TMs) (TM = Cu, Co, Ni, and Fe) is an extensively and efficiently used strategy to improve the electrocatalytic properties of Pt-based electrocatalysts. The alloying has an electronic effect (i.e., ligand effect and strain effect) in tuning the d-band center of Pt, which can effectively modify the binding strength of reactants (O 2 , methanol, and/or H 2 O), intermediate species, and products, thus improving the ORR/MOR properties. − Furthermore, the high oxophilicity of 3d TMs facilitates water dissociation and OH ad adsorption to produce a synergistic effect, or a bifunctional mechanism that is triggered by the Pt-M dual active site, which is important for the ORR/MOR performance. − Although large progresses have been made for the ORR and MOR in acidic, or alkaline, electrolytes by forming nanoalloys with Pt and 3d TMs, rare Pt-based electrocatalysts with a significant activity enhancement toward synchronous ORR and MOR in both acidic and alkaline electrolytes have been reported. − …”