Kulkarni Viveka K, Khiarak Behnam Nourmohammadi, Takano Shinjiro, Malola Sami, Albright Emily L, Levchenko Tetyana I, Aloisio Mark D, Dinh Cao-Thang, Tsukuda Tatsuya, Häkkinen Hannu, Crudden Cathleen M
Department of Chemistry, Queen's University, Chernoff Hall, Kingston, Ontario K7L 3N6, Canada.
Department of Chemical Engineering, Queen's University, Dupuis Hall, Kingston, Ontario K7L 3N6, Canada.
J Am Chem Soc. 2022 May 25;144(20):9000-9006. doi: 10.1021/jacs.2c00789. Epub 2022 May 12.
Atomically precise hydrido gold nanoclusters are extremely rare but interesting due to their potential applications in catalysis. By optimization of molecular precursors, we have prepared an unprecedented N-heterocyclic carbene-stabilized hydrido gold nanocluster, [Au(NHC)ClH]. This cluster comprises a dimer of two Au kernels, each adopting an icosahedral shape with one missing vertex. The two kernels are joined through triangular faces, which are capped with a total of three hydrides. The hydrides are detected by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy, with density functional theory calculations supporting their position bridging the six uncoordinated gold sites. The reactivity of this AuH cluster in the electrocatalytic reduction of CO is demonstrated and benchmarked against related catalysts.
原子精确的氢化金纳米团簇极为罕见，但因其在催化领域的潜在应用而备受关注。通过优化分子前驱体，我们制备出了一种前所未有的氮杂环卡宾稳定的氢化金纳米团簇[Au(NHC)ClH]。该团簇由两个金核二聚体组成，每个金核呈二十面体形状，缺少一个顶点。两个金核通过三角形面相连，面上总共覆盖有三个氢化物。通过电喷雾电离质谱和核磁共振光谱检测到了氢化物，密度泛函理论计算支持它们位于六个未配位金位点之间的桥连位置。展示了这种AuH团簇在电催化还原CO中的反应活性，并与相关催化剂进行了对比。
