Rhodium nanocrystals on porous graphdiyne for electrocatalytic hydrogen evolution from saline water

Abstract

The realization of the efficient hydrogen conversion with large current densities at low overpotentials represents the development trend of this field. Here we report the atomic active sites tailoring through a facile synthetic method to yield well-defined Rhodium nanocrystals in aqueous solution using formic acid as the reducing agent and graphdiyne as the stabilizing support. High-resolution high-angle annular dark-field scanning-transmission electron microscopy images show the high-density atomic steps on the faces of hexahedral Rh nanocrystals. Experimental results reveal the formation of stable sp–C~Rh bonds can stabilize Rh nanocrystals and further improve charge transfer ability in the system. Experimental and density functional theory calculation results solidly demonstrate the exposed high active stepped surfaces and various metal atomic sites affect the electronic structure of the catalyst to reduce the overpotential resulting in the large-current hydrogen production from saline water. This exciting result demonstrates unmatched electrocatalytic performance and highly stable saline water electrolysis.

Electronic Oxide–Support Strong Interactions in the Graphdiyne-Supported Cuprous Oxide Nanocluster Catalyst

“…On one hand, GDY has abundant alkyne moieties, which enable the formation of particular interfacial Cu–(sp)C bonds. On the other hand, GDY has the ability as an electron donor or acceptor, which enables both electron transfer directions depending on the work function and the interfacial bonding way. , …”

“…On the other hand, GDY has the ability as an electron donor or acceptor, which enables both electron transfer directions depending on the work function and the interfacial bonding way. 37,38 In order to further study the electronic interaction in Cu 2 O NCs/GDY, a control sample of graphene-supported Cu 2 O NCs with similar sizes was also prepared (the detailed synthesis and characterizations are shown in the experimental section and Figure S4). C 1s XPS and Raman spectra show no binding shift after loading Cu 2 O NCs, suggesting that there is no or very weak electron transfer and interaction between Cu 2 O NCs and GR (Figure 2c,d).…”

A novel graphdiyne (CnH2n−2) preparation strategy: calcium carbide-derived graphdiyne film supported cobalt tetroxide nanoneedles for photocatalytic hydrogen production

“…Its structure is formed by countless 18-C hexagonal structure composed of aromatic rings and acetylene bonds, so it is known as the most stable synthetic carbon material containing the diacetylene structure. 27–31 The unique π -conjugated network structure of GDY leads to uniform pore distribution and adjustable chemical and photoelectric characteristics, which makes it widely used in catalysis, energy, electronic devices, biomedicine and other fields. 32,33 The first organic method for preparing GDY was proposed and implemented by Li Yuliang's research group.…”

Synthesis of graphdiyne on a copper substrateviaa self-coupling reaction

“…33,34 Meanwhile, ion storage and molecular reactions are provided by the enormous tunnels and interspaces of the porous networks and macro/mesopore second-order structure. 19,35 In this work, the catalytic performance for the HER and the OER of the as-prepared GDY was also investigated using a threeelectrode system in 1 M KOH aqueous solution, and the testing data were adjusted to the reversible hydrogen electrode (RHE) in light of the Nernst equation. It is noteworthy that the GDY grown on the copper foil was used directly as the working electrode without any extra treatment.…”

“…GDY displays a similar electrochemical activity to that in former investigations. [33][34][35][36][37][38] Integrated with our previous studies, we propose not only a novel synthesis route for large-scale film formation but a potential method for the massive industrial preparation of GDY and its analogues.…”