Framing Silver Nanocrystals with a Second Metal to Enhance Shape Stability and Expand Functionality
Framing Silver Nanocrystals with a Second Metal to Enhance Shape Stability and Expand Functionality
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用第二种金属构建银纳米晶体以增强形状稳定性并扩展功能
DOI：
10.1021/accountsmr.1c00269
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发表时间：
2022
影响因子：
14.6
通讯作者：
Qin, Dong
中科院分区：
文献类型：
--
作者：
Qin, Dong
结论银纳米晶具有广泛的应用前景，但由于银原子在边缘和顶点等高能位置的溶解而导致形状不稳定，其性能趋于恶化。这个问题可以通过用更稳定的金属M框住颗粒以产生Ag@M核-框结构来解决。除了形状稳定性的改善之外，金属M的包含扩展了Ag纳米晶体的功能和能力。本帐户的第一部分介绍了两种策略的合理合成银基核框架纳米立方体。在第一种策略中，金属M的前体与Ag+离子在抗坏血酸（H2 Asc，还原剂）和聚（乙烯基吡咯烷酮）（PVP，胶体稳定剂）的存在下在环境条件下共滴定到Ag纳米立方体的水性悬浮液中。来自两种前体的M和Ag原子优先沿Ag纳米立方体的边缘共沉积沿着，用于产生Ag@M-Ag核-框架纳米立方体。第二种策略结合了从Ag纳米立方体的侧面雕刻Ag和以正交方式在边缘上同时沉积M和Ag原子。在一个方案中，在环境条件下，在H2 Asc、氢氧化钠（pH调节剂）和十六烷基三甲基氯化铵（胶体稳定剂和表面封端剂）的存在下，将M的前体滴定到Ag纳米立方体的水性悬浮液中。在另一方案中，在升高的温度下将前体滴定到Ag纳米立方体、PVP（胶体稳定剂和表面封端剂）和乙二醇（溶剂和还原剂）的混合物中。在这两种情况下，Ag原子通过氧化蚀刻从侧面雕刻，而来自化学还原的M和Ag原子共沉积在边缘上，用于生成Ag@M-Ag核框架凹纳米立方体。本帐户的第二部分展示了银基核框架纳米晶体的增强特性，以及一些新的功能。第一个例子演示了如何在高温下通过用Ir框架钝化脆弱的边缘来保持Ag纳米立方体的形状。第二个例子强调了使用Ag-Pd核框架纳米立方体作为Sers探针，用于原位监测Pd催化的NaBH 4还原4-硝基苯硫酚为4-氨基苯硫酚以及随后的Ag催化的空气中的氧气氧化4-ATP为反式-4，4 ′-二巯基偶氮苯。第三个实施例建立了通过位点选择性电流置换反应将Ag@Au-Au核框架凹纳米立方体转化为三金属笼状立方体的方法。总之，这些研究表明，银纳米晶体的形状稳定性可以提高，同时引入新的功能，通过框架其边缘与不同的金属。
ConspectusSilver nanocrystals embrace fascinating properties for a wide variety of applications, but their performance tends to deteriorate because of shape instability arising from the dissolution of Ag atoms from high-energy sites such as edges and vertices. This issue can be addressed by framing the particle with a more stable metal M for the generation of a Ag@M core-frame nanocrystal. In addition to the improvement in shape stability, the inclusion of metal M expands the functionality and capability of the Ag nanocrystals. The first part of this Account introduces two strategies for the rational synthesis of Ag-based core-frame nanocubes. In the first strategy, a precursor to metal M is cotitrated with Ag+ions into an aqueous suspension of Ag nanocubes in the presence of ascorbic acid (H2Asc, reducing agent) and poly(vinylpyrrolidone) (PVP, colloidal stabilizer) under ambient conditions. The M and Ag atoms derived from the two precursors are preferentially codeposited along the edges of Ag nanocubes for the creation of Ag@M-Ag core-frame nanocubes. The second strategy combines the carving of Ag from the side faces of Ag nanocubes and the concurrent deposition of M and Ag atoms on the edges in an orthogonal fashion. In one protocol, the precursor to M is titrated into an aqueous suspension of Ag nanocubes in the presence of H2Asc, sodium hydroxide (pH modifier), and cetyltrimethylammonium chloride (colloidal stabilizer and surface capping agent) under ambient conditions. In another protocol, the precursor is titrated into a mixture of Ag nanocubes, PVP (colloidal stabilizer and surface capping agent), and ethylene glycol (solvent and reducing agent) at an elevated temperature. In both cases, Ag atoms are carved from the side faces via oxidative etching while M and Ag atoms derived from the chemical reduction are codeposited on the edges for the generation of Ag@M-Ag core-frame concave nanocubes. The second part of this Account showcases the augmented properties of the Ag-based core-frame nanocrystals, in addition to some new functionality. The first example demonstrates how to preserve the shape of Ag nanocubes at an elevated temperature by passivating the vulnerable edges with Ir frames. The second example highlights the use of Ag–Pd core-frame nanocubes as a SERS probe for in situ monitoring the Pd-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol by NaBH4and the subsequent Ag-catalyzed oxidation of 4-ATP totrans-4,4′-dimercaptoazobezene by the oxygen from air. The third example establishes a method for the transformation of Ag@Au–Au core-frame concave nanocubes into trimetallic cage cubes through a site-selective galvanic replacement reaction. Altogether, these studies demonstrate that the shape stability of Ag nanocrystals can be enhanced while introducing new functionality by framing their edges with a different metal.
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影响因子：
15
作者：
Xia, Xiaohu;Zeng, Jie;Oetjen, L. Kyle;Li, Qingge;Xia, Younan
通讯作者：
Xia, Younan
DOI：
--
发表时间：
1987
期刊：
影响因子：
--
作者：
H. Nakatsuji;M. Hada;T. Yonezawa
通讯作者：
T. Yonezawa
影响因子：
8.6
作者：
Luo Zhang;Yun Zhang;Jaewan Ahn;Xin Wang;D. Qin
通讯作者：
Luo Zhang;Yun Zhang;Jaewan Ahn;Xin Wang;D. Qin
影响因子：
3.7
作者：
Xia, Xiaohu;Zeng, Jie;Zhang, Qiang;Moran, Christine H.;Xia, Younan
通讯作者：
Xia, Younan
影响因子：
62.1
作者：
Rycenga, Matthew;Cobley, Claire M.;Zeng, Jie;Li, Weiyang;Moran, Christine H.;Zhang, Qiang;Qin, Dong;Xia, Younan
通讯作者：
Xia, Younan