Engineering the Coordination Environment of Single‐Atom Platinum Anchored on Graphdiyne for Optimizing Electrocatalytic Hydrogen Evolution

Abstract

TwoP ts ingle-atom catalysts (SACs) of Pt-GDY1 and Pt-GDY2 were prepared on graphdiyne (GDY)supports. The isolated Pt atoms are dispersed on GDYt hrough the coordination interactions between Pt atoms and alkynyl C atoms in GDY, with the formation of five-coordinated C 1 -Pt-Cl 4 species in Pt-GDY1 and four-coordinated C 2 -Pt-Cl 2 species in Pt-GDY2. Pt-GDY2 shows exceptionally high catalytic activity for the hydrogen evolution reaction (HER), with am ass activity up to 3.3 and 26.9 times more active than Pt-GDY1 and the state-of-the-art commercial Pt/C catalysts, respectively.P t-GDY2 possesses higher total unoccupied density of states of Pt 5d orbital and close to zero value of Gibbsfree energy of the hydrogen adsorption (j DG Pt H* j)atthe Pt active sites,w hich are responsible for its excellent catalytic performance.T his work can help better understand the structure-catalytic activity relationship in Pt SACs.

Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance

“…SACs could be transferred to four-coordinated C2-Pt-Cl2 SACs for optimized electrocatalytic hydrogen evolution, as reported by Si et al using graphdiyne as supports [58].…”

“…As for pure carbon materials as substrates of SACs, most active atoms are selectively embedded on the defects of carbon substrates, which exhibited as carbon coordinated SACs. For example, single metal atoms such as Ni, Pd and Pt metal atoms embedded on pure graphene or graphdiyne have been reported by Chen et al [56], Lu et al [57] and Lu et al [58]. However, due to the low binding energy between C and metal atoms (the lack of lone electron pair in C atom), SACs on pure carbon substrates usually are synthesized at high annealing temperature and feature low loading amount.…”

Microenvironment modulation of single-atom catalysts and their roles in electrochemical energy conversion

“…Microenvironment engineering of atomically dispersed metal sites anchored on various carbon-based hosts has also attracted great interest in HER (125)(126)(127)(128)(129)(130)(131)(132)(133). For instance, Liu et al (134) developed onion-like nanospheres of carbon (OLC)-supported single Pt atom (Pt 1 /OLC SAC) as a highly efficient HER catalyst.…”

Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production

“…Single-atom heterogeneous catalysts (SACs), containing spatially isolated metal atoms stabilised on appropriate hosts, have emerged as a promising class of materials with diverse applications in chemical transformations [1][2][3][4][5] and energy conversion. [6][7][8] Owing to the increased active site uniformity and the possibility to tune the coordination environment through adapting the host structure, [9][10][11][12][13] SACs are uniquely suited to derive structure-performance relationships and gain mechanistic understanding of complex catalytic transformations, a prerequisite for the design of highperformance catalysts, needed to meet the sustainability goals of modern society. 14 A prominent example is vinyl chloride manufacture via acetylene hydrochlorination, a longestablished industrial process which runs over highly toxic and volatile mercury-based catalysts, causing severe consequences for human health and the environment.…”