Chen-Wei Liu (劉鎮維)
NDHU chair professor, Department of Chemistry, National Dong Hwa University,
Hualien, Taiwan 97401
chenwei@gms.ndhu.edu.tw
Hydride-doped Coinage Metal Nanoclusters: From Superatomic Alloys to Superclusters
Hydride, H- (1s2), the smallest closed shell anion, is a one-negative charge ligand widely used to stabilize metallic compounds. Aside from its characteristic NMR signals, detailed characterizations of hydride location within metal clusters are problematic due to its near-invisible X-ray scattering length. Therefore, chemists working on polyhydrido metal clusters must be very cautious. In 2009, the Liu group first succeeded in the isolation of a hydride insertion product, Cu8(H)L6 (L = E2PR2, E = S, Se), where significant metal kernel distortions compared to an empty CuI 8 cube (stabilized by six dichalcophosphate ligands) suggested the additional hydride was located at the center of Cu8 cage. This work kicks off the chemistry of coinage metal hydrides created by the Liu group. During a span of 17 years, we have uncovered four important concepts: (1) hydride additions can assist the growth of nanoscale copper clusters, (2) interstitial hydrides in nanoclusters can reduce M(I) (M = Cu, Ag, Au) to M(0) and form stable superatoms, (3) the interstitial hydride coordinated to Ni, Pd, Pt, Rh, Ir, Ru within Ag- and Cu-rich clusters can behave as “metallic” hydrogen (i.e. to provide its 1s(H) electron to the cluster electron count), (4) the first synthesis of a three-dimensional self-assembled supercluster formed by the tetrahedral arrangement of four IrH2@Ag12 icosahedra, reminiscent of a tetrahedrane. This presentation will focus on the synthesis, structures, and bonding of hydride-doped precious metal nanoclusters, which are indeed structurally precise, ultra-small nanoparticles, as well as its remarkable HER activities catalyzed by a 2-electron palladium(platinum)/copper superatomic alloy, [Pd/Pt/HCu11{S2P(OiPr)2}6(C≡CPh)4].
References
[1] Dhayal, R. S.; van Zyl, W. E.; Liu, C. W. Acc. Chem. Res. 2016, 49, 86 – 95.
[2] Sharma, S.; Chakrahari, K. K.; Saillard, J.-Y.; Liu, C. W. Acc. Chem. Res. 2018, 51, 2475 – 2483.
[3] Artem’ev, A. V.; Liu, C. W. Chem. Commun. 2023, 59, 7182 – 7195.
[4] Chiu, T.-H.; Liao, J.-H.; Silalahi, R. P. B.; Pillay, M. N.; Liu, C. W. Nanoscale Horiz. 2024, 9, 675 – 692.
Contact : Camille Latouche (MIOPS)
