biostudies-literatureUnknown3(9)Zhuang SThe 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-<i>tert</i>-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).Precision chemistry516-524https://www.ebi.ac.uk/biostudies/studies/S-EPMC12458030biostudies-literatureAtomically Precise Fcc-Amorphous Homometal Heterojunction with ∼1 nm Size.PMC12458030Wu ZLiao LYang JWang PLi JZhuang SYou QPei YDeng HChen DfalseAtomically Precise Fcc-Amorphous Homometal Heterojunction with ∼1 nm Size.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-<i>tert</i>-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).2025-01-01T00:00:00Z2025 Sep2026-06-03T20:15:51.261Z2026-05-30T03:06:57.168ZS-EPMC124580304100109010.1021/prechem.5c00006