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. 2025 Nov 5;147(44):40205-40213.
doi: 10.1021/jacs.5c08684. Epub 2025 Oct 23.

Motif Editing Reveals Hidden Active Sites in Atomically Precise Metal Nanoclusters for Enhanced Electrocatalysis

Zhihe Liu  1   2 , Moshuqi Zhu  3   4 , Bo Li  5 , Junmei Chen  6 , Shibo Xi  7 , Yang-Yang Yu  8 , Lu Xia  6 , Lei Wang  1   2 , De-En Jiang  5 , F Pelayo García de Arquer  6 , Jianping Xie  1   2   4
Affiliations

Motif Editing Reveals Hidden Active Sites in Atomically Precise Metal Nanoclusters for Enhanced Electrocatalysis

Zhihe Liu et al. J Am Chem Soc. .

Abstract

Metal nanoclusters offer atomically precise platforms for catalysis but often require bulk molecular motifs to achieve cluster stability. Here, we assess how these motifs block access to active sites and quantify trade-offs between structural integrity and catalytic performance. Based on this, we designed a motif-by-motif surface editing strategy to expose catalytic sites with atomic precision while preserving the kernel integrity of the cluster. Using [Au25(pMBA)18]- nanoclusters (pMBA = para-mercaptobenzoic acid) as a model system, we selectively replace sterically bulky Au2(pMBA)3 motifs with compact Cu-(pMBA)3 units, yielding [Au13Cu4(pMBA)12]3- nanoclusters with a symmetric, open-surface architecture. In situ absorption and mass spectrometry reveals a stepwise motif exchange mechanism distinct from conventional coreduction or ligand displacement, which enables surface reconstruction without kernel distortion. The resulting clusters deliver a 180-fold enhancement in hydrogen evolution turnover frequency (18.8 s-1), compared to the parent [Au25(pMBA)18]- (0.1 s-1), attributed to increased Au3 facet exposure and improved hydrogen binding, as suggested by spectroscopy and density functional theory. This work offers a generalizable route to programmable surface engineering in metal nanoclusters, contributing to advance in the longstanding paradox between atomic precision and catalytic accessibility.

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Figures

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Structural characterization of motif-edited Au nanoclusters with kernel retention and facet exposure. (a) Schematic illustration of the surface motif editing strategy, transforming [Au25(pMBA)18]− into [Au13Cu4(pMBA)12]3– via rational substitution of Au2(pMBA)3 motifs by compact Cu-(pMBA)3 units, thereby exposing previously blocked Au3 facets on the icosahedral kernel. Right: the number of solvent-accessible Au3 facets increases from 2 to 16 (out of 20 total). (b) Ultraviolet–visible absorption spectra comparing [Au25(pMBA)18]− (blue) into [Au13Cu4(pMBA)12]3– (red). Insets: photographs of aqueous cluster solutions. (c) ESI-MS of [Au25(pMBA)18]− displaying intact cluster signals (e.g., [M–2H]3–), with inset showing agreement between simulated and experimental isotopic distributions. (d) ESI-MS of [Au13Cu4(pMBA)12]3– with a dominant peak at m/z = 1550.9 and a matching simulated isotope pattern (inset), confirming its formula. (e) Tandem MS of [Au13Cu4(pMBA)12]3– reveals a fragmentation product corresponding to loss of a Cu-(pMBA)3 unit under 20 eV collision energy, validating the presence of discrete surface motifs.
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Structure correlation between [Au25 (pMBA)18]− and [Au13Cu4(pMBA)12]3– NCs. (a) 1H nuclear magnetic resonance spectra of [Au13Cu4(pMBA)12]3– compared to [Au3Cu2(pMBA)6]−. (b) Fourier-transform k3-weighted Au L3 edge extended X-ray absorption fine structure (FT-EXAFS) spectra for [Au25(pMBA)18]− and [Au13Cu4(pMBA)12]3–, showing the preservation of Au–S coordination upon motif editing. (c) FT-EXAFS analysis at Cu K-edge for Cu-(pMBA) complex and [Au13Cu4(pMBA)12]3–, confirming exclusive Cu–S coordination and the absence of Au–Cu bonding. (d–f), DFT-optimized structural models of [Au13Cu4(pMBA)12]3–, featuring an icosahedral Au13 kernel decorated with four Cu-(pMBA)3 motifs in trigonal planar configurations (yellow = Au, red = Cu, light yellow = S, gray stick = pMBA ligand).
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Elucidating the transformation pathway from [Au25(pMBA)18]− to [Au13Cu4(pMBA)12]3– via stepwise surface motif editing. (a) Time-resolved UV–vis absorption spectra showing the disappearance of kernel-motif hybrid bands at ca. 430 and 470 nm and preservation of Au13 kernel signals at ca. 630 and 700 nm, indicating motif transformation without kernel disruption. (b) Corresponding in situ ESI-MS tracking reveals the rapid formation of [Au13Cu4(pMBA)12]3– within 5 min, accompanied by transient intermediates. (c) UV–vis spectra of the stepwise reaction reveals a progressive decline in motif-associated absorptions with incremental Cu-(pMBA) addition. (d) ESI-MS analysis uncovers the formation of distinct intermediates, and (e) Corresponding peak intensity profiles of precursors and intermediates.
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Electrocatalytic HER performance of [Au25(pMBA)18]− and [Au13Cu4(pMBA)12]3– NCs. (a) Tafel plots derived from LSV curves, highlighting enhanced HER kinetics upon motif editing. (b) In situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINER) showing the potential-dependent intensity of the Au–H stretching vibration in [Au13Cu4(pMBA)12]3–. DFT-optimized structure with calculated H* adsorption energy of (c) [Au25(pMBA)18]− (active sites: Au3 facets) and (d) of [Au13Cu4(pMBA)12]3– (active sites: Au and Cu center) (Ligands omitted for clarity, color codes: yellow = Au, red = Cu, light yellow = S, blue = H). (e) Comparative performance metrics including current density at η = 200 mV, Au-normalized mass activity, turnover frequency, and electrical conductance, underscoring the synergistic enhancement in catalytic activity upon motif editing.
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Structural and electrochemical stability of [Au13Cu4(pMBA)12]3– NCs during HER. (a) Chronoamperometric stability test at – 0.32 V (vs RHE) over 60 h, showing consistent current density. (b, c), Au L3-edge and Cu K-edge XANES spectra of [Au13Cu4(pMBA)12]3– recorded pre- and post-HER, indicating unchanged oxidation states. (d, e) Corresponding FT-EXAFS spectra at the Au and Cu edges, confirming retention of local bonding environments. (f) DFT optimized structure of [Au13Cu4(pMBA)12]3–, showing trigonal-planar Cu-(pMBA)3 surface motifs anchored on the icosahedral Au13 kernel (ligands omitted for clarity; color code: green = Au, blue = Cu, yellow = S; triangles mark Cu-(pMBA)3 motifs).
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