Structured copper-hydride nanoclusters provide insight into the surface-vacancy-defect to non-defect structural evolution.
Structured copper-hydride nanoclusters provide insight into the surface-vacancy-defect to non-defect structural evolution.
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结构化氢化铜纳米团簇提供了对表面空位缺陷到无缺陷结构演变的深入了解
DOI：
10.1039/d2sc03239b
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发表时间：
2022-12-14
期刊：
影响因子：
8.4
通讯作者：
中科院分区：
文献类型：
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作者：
探索具有相似尺寸和原子数的团簇由于去除或添加少量原子而引起的结构演化有助于深入理解结构-性质关系。本文报道了三种表征良好的铜氢化物纳米团簇，它们提供了对表面空位缺陷到非缺陷结构演化的深入了解。采用一锅法在温和条件下合成了具有单一C1对称轴的表面缺陷型氢化铜纳米团簇[Cu 28（S-c-C6 H11）18（PPh 2 Py）3 H8]2+（简称Cu 28-PPh 2 Py），并对其结构进行了表征.通过配体调控，将第29个铜原子插入到表面空位位，得到两个无缺陷的氢化铜纳米团簇，即[Cu29（SAdm）15Cl3（P（Ph-Cl）3）4H10]+（Cu29-P（Ph-Cl）3）和（Cu29（S-c-C6H11）18（P（Ph-pMe）3）4H10）+（Cu29-P（Ph-Me）3）。优化后的结构表明，Cu 29-P（Ph-Me）3的立方八面体Cu 13核为10个帽的四个三角形和六个正方形平面结构，而Cu 29-P（Ph-Cl）3的反立方八面体Cu 13核为10个帽的四个三角形和六个正方形平面结构，其中Cu 28-PPh 2 Py中的八个环覆盖其反立方八面体Cu 13核的四个三角形和四个正方形平面结构。从Cu 28-PPh 2 Py到Cu 29-P（Ph-Cl）3再到Cu 29-P（Ph-Me）3，簇合物的稳定性依次增加，表明簇合物的稳定性受簇合物整体结构的影响.对金属核、壳和核-壳键合模型的结构调整，从Cu 28-PPh 2 Py移动到Cu 29-P（Ph-Cl）3，然后移动到Cu 29-P（Ph-Me）3，使得能够理解负责其物理化学性质的结构演变和机制，并对铜纳米团簇中的表面空位结构和结构-性质关系提供有价值的见解。从表面空位缺陷Cu 28-PPh 2 Py到无缺陷Cu 29-P（Ph-Cl）3和Cu 29-P（Ph-Me）3的结构调整为铜纳米团簇中表面空位的结构和结构-性质关系提供了有价值的见解。
Exploring the structural evolution of clusters with similar sizes and atom numbers induced by the removal or addition of a few atoms contributes to a deep understanding of structure–property relationships. Herein, three well-characterized copper-hydride nanoclusters that provide insight into the surface-vacancy-defect to non-defect structural evolution were reported. A surface-defective copper hydride nanocluster [Cu28(S-c-C6H11)18(PPh2Py)3H8]2+ (Cu28-PPh2Py for short) with only one C1 symmetry axis was synthesized using a one-pot method under mild conditions, and its structure was determined. Through ligand regulation, a 29th copper atom was inserted into the surface vacancy site to give two non-defective copper hydride nanoclusters, namely [Cu29(SAdm)15Cl3(P(Ph-Cl)3)4H10]+ (Cu29-P(Ph-Cl)3 for short) with one C3 symmetry axis and (Cu29(S-c-C6H11)18(P(Ph-pMe)3)4H10)+ (Cu29-P(Ph-Me)3 for short) with four C3 symmetry axes. The optimized structures show that the 10 hydrides cap four triangular and all six square-planar structures of the cuboctahedral Cu13 core of Cu29-P(Ph-Me)3, while the 10 hydrides cap four triangular and six square-planar structures of the anti-cuboctahedral Cu13 core of Cu29-P(Ph-Cl)3, with the eight hydrides in Cu28-PPh2Py capping four triangular and four square planar-structures of its anti-cuboctahedral Cu13 core. Cluster stability was found to increase sequentially from Cu28-PPh2Py to Cu29-P(Ph-Cl)3 and then to Cu29-P(Ph-Me)3, which indicates that stability is affected by the overall structure of the cluster. Structural adjustments to the metal core, shell, and core–shell bonding model, in moving from Cu28-PPh2Py to Cu29-P(Ph-Cl)3 and then to Cu29-P(Ph-Me)3, enable the structural evolution and mechanism responsible for their physicochemical properties to be understood and provide valuable insight into the structures of surface vacancies in copper nanoclusters and structure–property relationships. Structural adjustments in moving from surface-vacancy-defect Cu28-PPh2Py to non-defect Cu29-P(Ph-Cl)3 and Cu29-P(Ph-Me)3 provide valuable insight into the structures of surface vacancies in copper nanoclusters and structure–property relationships.
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影响因子：
8.4
作者：
Chakrahari KK;Silalahi RPB;Liao JH;Kahlal S;Liu YC;Lee JF;Chiang MH;Saillard JY;Liu CW
通讯作者：
Liu CW
影响因子：
16.6
作者：
Dhayal, Rajendra S.;Liao, Jian-Hong;Liu, C. W.
通讯作者：
Liu, C. W.
影响因子：
16.6
作者：
Chakrahari, Kiran Kumarvarma;Liao, Jian-Hong;Liu, C. W.
通讯作者：
Liu, C. W.
影响因子：
16.6
作者：
通讯作者：
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影响因子：
2.1
作者：
Dhayal, Rajendra S.;Chen, Hsuan-Ping;Liu, C. W.
通讯作者：
Liu, C. W.