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首页> 外文期刊>Catalysis science & technology >Synthesis of gold nanocrystals with chiral morphology, chiral ligand and more exposed high-index facets as electrocatalyst for the oxidation of glucose enantiomers with high enantioselectivity and catalytic activity
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Synthesis of gold nanocrystals with chiral morphology, chiral ligand and more exposed high-index facets as electrocatalyst for the oxidation of glucose enantiomers with high enantioselectivity and catalytic activity

机译：具有手性形态的金纳米晶体的合成，手性配体和更暴露的高索引方面，作为具有高映射性和催化活性的葡萄糖对映体氧化的电催化剂

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The poor enantioselectivity and catalytic activity of chiral metal nanocrystals limit their wide applications in chiral synthesis. In this study, we report a strategy for the synthesis of chiral gold nanocrystals via the reduction of HAuCl4 with ascorbic acid in the presence of CTAC, KBr and KI to form trioctahedral gold nanocrystals and their asymmetric structural evolution induced by d/l-cysteine. The resulting gold nanocrystals offer unique structures with a chiral morphology, chiral ligand and more exposed high-index facets. The formed d-Cys-Au and l-Cys-Au under optimized conditions exhibited high enantioselectivity and catalytic activity for the catalytic oxidation of glucose enantiomers. The catalytic activity of d-Cys-Au for l-glucose was 3.1-fold higher than that for d-glucose. The catalytic activity of l-Cys-Au for d-glucose was 3.4-fold higher than that for l-glucose. The DPV current of d-Cys-Au linearly increased and the DPV current of l-Cys-Au linearly decreased with an increase in the l-glucose/d-glucose ratio. The catalytic behavior of gold nanocrystals highly depend on the chiral morphology and chiral ligand. l-Cys-Au prepared with an evolution time of 20 min exhibited the best enantioselectivity. The increase in the coverage of l-cystine on l-Cys-Au resulted in reduced catalytic activity but improved enantioselectivity. The introduction of l-ascorbic acid hardly affected the catalytic activity of l-Cys-Au for d-glucose but obviously decreased the catalytic activity for l-glucose.
机译：手性金属纳米晶体的对映选择性和催化活性不足，限制了其在手性合成中的广泛应用。在这项研究中，我们报告了一种在存在CTAC，KBR和KI存在下用抗坏血酸还原Haucl4合成手性金纳米晶体的策略，以形成三十二十体金纳米晶体及其由D/L-Cysteine诱导的不对称结构进化。由此产生的金纳米晶体提供具有手性形态，手性配体和更裸露的高索引方面的独特结构。在优化的条件下形成的D-CYS-AU和L-CYS-AU表现出高的对映选择性和催化活性，用于葡萄糖对映体的催化氧化。 D-CYS-AU对L-葡萄糖的催化活性比D-葡萄糖高3.1倍。 L-CYS-AU对D-葡萄糖的催化活性比L-葡萄糖高3.4倍。 D-CYS-AU的DPV电流线性增加，L-Cys-AU的DPV电流随着L-葡萄糖/D-葡萄糖比的增加而线性降低。金纳米晶体的催化行为高度取决于手性形态和手性配体。以20分钟的演化时间制备的L-Cys-AU表现出最佳的对映选择性。 L-Cystine在L-Cys-AU上的覆盖率增加导致催化活性降低，但改善了对映选择性。 L-甲酸的引入几乎不会影响L-Cys-AU对D-葡萄糖的催化活性，但显然会降低L-葡萄糖的催化活性。

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