Ultrafine Pt Nanoclusters Confined in a Calixarene-Based {Ni₂₄} Coordination Cage for High-Efficient Hydrogen Evolution Reaction

Abstract

To obtain stable and ultrafine Pt nanoclusters, a trigonal prismatic coordination cage with the sulfur atoms on the edges was solvothermally synthesized to confine them. In the structure of {Ni(TC4A-SO)(TDC) (HO)} (HTC4A-SO = p-tert-butylsulfonylcalix[4]arene; HTDC = 2,5-thiophenedicarboxylic acid), three Ni-(TC4A-SO) SBUs are bridged by three TDC ligands into a triangle and two such triangles are pillared by three pairs of TDC ligands to form a trigonal prism. The cage cavity has 12 sulfur atoms on the surface. Because of the porous structure and strong covalent interaction between metal and sulfur, ultrafine Pt nanoclusters composed of less than ∼18 Pt atoms can be facilely confined in the present trigonal prismatic cage (Pt@CIAC-121). The as-synthesized Pt NCs exhibit higher electrocatalytic activity than commercial Pt/C toward hydrogen evolution reaction.

Supramolecular Maleate Adducts of Copper(II) 12‐Metallacrown‐4: Magnetism, EPR, and Alcohol Sorption Properties

“…Polynuclear complexes and supramolecular assemblies with porous lattices based on polynuclear blocks are attracting attention as the potential basis for multifunctional materials due to their ability to absorb different substrates, as well as other physical properties Inasmuch as the properties of the starting compound – the “building block” – usually pre‐determine the properties of the resultant coordination polymer or supramolecular assembly based on it, the choice of building block is important. The combination of physical and chemical properties of the chosen block with the ability of a porous lattice in the resulting compound to interact with certain substrates enables use of these assemblies as active constituents of sensors,, as magnetic, or luminescent, materials with tunable properties, as sorbents,, or in separation processes …”

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

“…[1][2][3] Among the developed electrocatalysts,P t-based catalysts are the most effective electrocatalysts for HER. [7,8] Compared with traditional Pt-based catalysts,P ts ingle-atom catalysts (SACs) have great advant-age with utmost utilization of Pt atoms,w hich can dramatically reduce the usage of noble metal Pt and decrease the cost of catalysts.I th as been shown that the isolated Pt atoms anchored on the surfaces of FeO x ,M oS 2 ,T iN,g -C 3 N 4 and graphene indeed exhibit much higher catalytic activity and much lower usage of noble Pt than the traditional Pt-based catalysts,s uch as Pt/C. Therefore,g reat efforts have been devoted to increase the platinum utilization as well as to improve the HER activity of Pt-based catalysts.…”

Recent Progresses in Electrocatalysts for Water Electrolysis

“…This effect of strong metal-support interactions (SMSI) can also be seen in electrocatalysis [238][239][240][241]. For example, Wang et al [239] synthesized ultrafine and stable Pt nanoclusters with a trigonal prismatic coordination cage with sulphur atoms on the edges and their electrochemical tests indicated that the synthesized Pt NCs possessed high electrocatalytic performances towards HERs with low overpotentials and high current densities.…”

“…For example, Wang et al [239] synthesized ultrafine and stable Pt nanoclusters with a trigonal prismatic coordination cage with sulphur atoms on the edges and their electrochemical tests indicated that the synthesized Pt NCs possessed high electrocatalytic performances towards HERs with low overpotentials and high current densities. This observed high catalytic activity was attributed to the highly active surface of the ultrafine Pt NCs and the synergistic effects between Pt NCs and the cage matrix [241]. The schematic illustration of the process used by Wang et al is shown in Fig.…”

“…g-h Polarization curve and Tafel slope [237]. b Illustration of the assembly of trigonal prismatic {Ni 24 } coordination cages (CIAC-121) and the fabrication of ultrafine Pt NCs [241] electrode surface [242]. In the case of HER catalytic activity, the activity is observed to follow a volcano-type relation in which the hydrogen binding free energy should be closest to that of state-of-the-art Pt catalysts (∆G H approximately zero).…”