Lingwen Liao

While topology–property relationships are well established in covalent two‐dimensional (2D) materials, their extension to metallic systems is hindered by the nondirectional nature of metallic bonding and an intrinsic tendency toward three‐dimensional (3D) close‐packed structures. Herein, we develop a Hub‐Driven Ring Fusion (HDRF) strategy for constructing extended metallic topologies beyond discrete motifs. Guided by this strategy, we synthesize an atomically precise Pd ₁₁ nanocluster featuring a rare fused tri‐pentagonal metal‐ring network. Magnetic shielding and nucleus‐independent chemical shift (NICS) analyses reveal pronounced spatial anisotropy and discontinuous shielding distributions, indicating a breakdown of global electronic coherence and the formation of partitioned electronic domains across fused rings. These “topology‐induced electronic domains” connectivity‐governed electronic fragmentation, rather than uniform delocalization, defines the intrinsic electronic landscape of the cluster and clarifies that it is not merely a simple size expansion of Pd ₅ . Pd ₁₁ exhibits significantly enhanced performance in the electrocatalytic hydrogenation of nitrobenzene, achieving 98.1% conversion, 97.4% aniline yield, and 99.3% selectivity, outperforming Pd ₅ and Pd ₈ clusters. Density functional theory (DFT) calculations further demonstrate that the fused tri‐pentagonal topology optimizes electron distribution, enhances interfacial reactivity, and lowers the overall reaction barrier, providing a mechanistic basis for the observed catalytic enhancement.

Versatile organic ligands can notably enhance the stability and tunability of metal nanoclusters (NCs), and, consequently, all-organic ligand–protected metal nanoclusters have recently attracted widespread attention. Platinum (Pt) remains an indispensable metal in various fields, particularly in catalysis and cancer therapeutics. However, all-organic ligand–protected Pt nanoclusters are rarely reported due to substantial synthesis challenges, which have hindered progress in Pt nanocluster research and their practical applications. Herein, we report the successful synthesis of the largest all-organic ligand–protected Pt nanocluster to date, [Pt19(NapNC)27][PF6]2 (abbreviated as Pt19; NapNC: isocyanonaphthalene), achieved through the development of a ligand-exchange method. Single-crystal X-ray diffraction (SC-XRD) revealed a face-centered cubic (FCC), nonequivalent structure that has not been previously documented for all-organic ligand–protected Pt nanoclusters. Compared with its partially organic parent nanoclusters, this novel nanocluster exhibits considerably enhanced stability in both the ground and excited states. Furthermore, the Pt19 nanocluster demonstrates superior activity in the electrocatalytic methanol oxidation reaction (MOR) relative to its parent nanoclusters and commercial Pt/C. Based on its well-defined structure, we gained deep insights into the exceptional MOR activity of Pt19 and revealed, for the first time, the steric and electronic preferences of the active sites for electrocatalytic MOR.

Metal nanoclusters have garnered significant attention owing to their unique physicochemical properties. However, the synthesis of reduced, reactive metal-based nanoclusters, such as reduced Ni nanoclusters, remains challenging because of their intrinsic instability. Herein, we first reported ambient-stable, reduced Ni nanoclusters by subtly engineering the protecting ligands, and particularly revealed a previously unrecognized stabilization mechanism in which two Ni nanoclusters, each difficult to isolate individually, are stabilized through coexistence. Remarkably, the paired clusters remain stable in both the solid and solution phases and exhibit interdependent stability reminiscent of obligate mutualism in biological systems. This finding suggests that weak intercluster interactions can be harnessed to engineer mutually stabilized assemblies, providing access to metal nanoclusters that would otherwise be unattainable. Further studies reveal that the two nanoclusters play complementary catalytic roles and synergistically promote nitrate reduction. Hydrogen spillover between the paired clusters facilitates catalytic turnover, resulting in markedly enhanced activity relative to the individual nanoclusters. These results demonstrate that nanocluster supra-assembly, beyond the specific case of obligate mutualism, can simultaneously enhance stability and functionality. More broadly, this work establishes intercluster assembly as a general strategy for accessing, stabilizing, and optimizing atomically precise nanoclusters, opening new opportunities for the rational design of advanced catalytic systems.

Hierarchical Pd–Cu nanowires with lattice-expanded Cu (100)/(111) interfaces were designed. Experimental and theoretical results demonstrate their superior activity toward the CO ₂ reduction reaction.

The rational design of a bimetallic nanostructure with a phase separation and interface is of great importance to enhance electrocatalytic performance. Herein, PdNi heterostructures with controlled elemental distributions were constructed via a seeded growth strategy. Partially coated Ni islands in the Pd-Ni nanowire and strained Pd branches in the Pd-NiPd nanowires are revealed, respectively. Impressively, Pd-NiPd nanowires with abundant branches exhibit a superior mass current density and cycling stability toward an ethanol oxidation reaction (EOR) and ethylene glycol oxidation reaction (EGOR). The highest mass activities of 8.63 A mg_Pd⁻¹ and 12.53 A mg_Pd⁻¹ for EOR and EGOR, respectively, are realized on the Pd-NiPd nanowires. Theoretical calculations indicate that the Pd (100)-PdNi (111) interface stands out as an active site for enhancing OH adsorption and the decreasing CO bonding interaction. This study not only puts forward a simple method to construct bimetallic nanostructures with desired elemental distributions and interfaces but also demonstrates the significance of interface engineering in regulating the catalytic activity of metallic nanomaterials.

Metastable crystal defects endow nanocrystals with optimized electronic configurations and remarkable electrocatalytic properties. Nevertheless, how the crystal defects, such as twin boundaries, regulate the nucleation and growth of multimetallic heterostructures requires further study. Herein, platinum-yttrium (PtY) alloys with a metastable twin structure were fabricated by overgrowth on Au nanoparticles, resulting in the formation of Au@PtY multibranched nanodendrites (Au₄₆Pt₄₀Y₁₄). The branched Au@PtY nanoparticle exhibits a Y-rich twin structure on the surface, as affirmed by both experimental investigation and theoretical calculation. Impressively, branched Au@PtY nanoparticles demonstrate superior mass activity and stability toward the alcohol oxidation reaction, compared to core-shell Au@PtY nanoparticles (Au₆₇Pt₂₅Y₈), PtY nanodendrites (Pt₇₃Y₂₇), and commercial Pt/C catalysts. Density functional theory calculations, together with operando infrared reflection absorption spectroscopy, suggest that the superior electrochemical characteristics could be ascribed to the Y-rich twin on the surface. This work opens the way for the rational design of heterometallic nanostructures with crystal defects for catalytic applications.

The emerging of ultrasmall gold nanoparticles (nanoclusters) with atomic precision provides opportunities for precisely studying crystalline–amorphous heterostructures, despite the construction of such structures being challenging. In this work, we developed an acid-induction method and synthesized a Au₅₂(TBBT)₃₀ (TBBTH = 4-tert-butylbenzenelthiol) nanocluster with the kernel composed of two parts: the amorphous Au₂₂ part and the fcc Au₂₁ part, which represents the first construction of fcc-amorphous homometal heterojunction with ∼1 nm size. Density function theory (DFT) revealed that the HOMO–LUMO majorly distributed in the amorphous part and the HOMO–LUMO gap was dominated by the amorphous part, indicating the redox activity of the amorphous Au₂₂ part in contrast to the fcc Au₂₁ part, which was experimentally confirmed by differential pulse voltammetry, antioxidation test and anti-Galvanic reaction. But for electro-catalyzing reduction of CO₂ to CO, the crystalline surface sites were revealed to be more catalytically active than the amorphous surface sites in catalyzing the reduction of CO₂ to CO, and the most active sites were assigned to the cosurface sites of amorphous Au₂₂ and fcc Au₂₁, which is also responsible for the high performance of Au₅₂(TBBT)₃₀ relative to the pure fcc-structured Au₅₂(TBBT)₃₂ (the highest CO FE: 96.7% at −0.67 V vs 73.3% at −0.57 V; CO partial current density at the corresponding potential: −7.3 vs −2.7 mA cm^–2).

Few reports on paramagnetic metal nanoparticles with atomic precision and their difficult tailoring retard the insightful investigation of metal nanoparticle paramagnetism. Herein, we introduced a thiol-iodine mixture ligand–protecting strategy to successfully synthesize multi-shell paramagnetic [Au ₁₂₇ I ₄ (TBBT) ₄₈ (I: iodine, TBBT: 4-tert-butylphenylthiolate)]. The innermost Au atom was successfully removed via thiol induction without altering the structure framework to produce diamagnetic Au ₁₂₆ I ₄ (TBBT) ₄₈ with local ligand arrangement changed (butterfly effect), which could be further transformed into paramagnetic [Au ₁₂₆ I ₄ (TBBT) ₄₈ ] ⁺ via hydrogen peroxide oxidation. The spin populations of both paramagnetic nanoparticles are more densely distributed on surface iodine than sulfur. Diamagnetic Au ₁₂₆ I ₄ (TBBT) ₄₈ exhibited a Faradaic efficiency of ~100% at −0.57 volt during the electrocatalytic reduction of carbon dioxide to carbon monoxide, while paramagnetic Au ₁₂₇ I ₄ (TBBT) ₄₈ and [Au ₁₂₆ I ₄ (TBBT) ₄₈ ] ⁺ exhibited the maximum Faradaic efficiency of 87% at −0.67 volt and 90% at −0.57 volt, respectively, indicating the spin-catalytic activity correlation.

Constructing multimetallic alloy heterostructures with the desired interface and phase separation is a promising method to optimize the electrochemical properties of noble metal nanomaterials. Nevertheless, tailoring the elemental distribution and lattice structures of such multimetallic nanomaterials still poses major difficulties. In this study, Cu-PtNi nanowires coupling PtNi with PtNiCu active sites are fabricated by seeded synthesis on a Cu template. Owing to the oxophilic nature of PtNi sites and the anti-CO poisoning capability of PtNiCu facets, the as-synthesized Cu-PtNi nanowires exhibit enhanced methanol oxidation reaction (MOR) performance (7.73 A mg_Pt^-1), outperforming those of PtNiCu alloy, PtNi alloy, and commercial Pt/C catalysts. Theoretical calculations in conjunction with operando infrared reflection absorption spectroscopy demonstrate that the lattice-compressed Pt₃Ni (111)-Pt₃NiCu (100) interface stands out as a highly efficient active site, which promotes OH intermediate adsorption and simultaneously weakens CO intermediate adsorption during the MOR. In addition, at 10 mA cm^-2, Cu-PtNi nanowires also exhibit an impressively reduced overpotential of 35.2 mV for the hydrogen evolution reaction (HER) under alkaline conditions. This work offers a strategy to boost the electrocatalytic performance of multimetallic nanomaterials.