金-银纳米异质组装过程的化学不相容性

doi:10.6023/A24040147

摘要/Abstract

通过自组装构筑不同金属纳米粒子间的异质组装体, 对于理解和调控等离激元近场耦合, 以及“点亮”等离激元光学暗态等具有重要意义. 利用组装体中不同金属的催化活性差异, 还可望实现协同或接力催化. 金和银纳米材料在可见光区具有强吸收和散射, 成为等离激元器件的常见选择. 由于银的化学性质较金活泼, 其胶体稳定性也不及金纳米粒子, 实际应用中远没有金纳米粒子普及. 与金相比, 银纳米粒子的带间跃迁与等离激元共振较为远离, 其等离激元损耗也更低, 呈现比金更强且更对称的等离激元共振峰, 展现出诱人的光学性质. 在自组装结构中同时引入金和银两种纳米砌块, 可望实现同质结构无法获得的功能. 然而, 由于两者具有显著不同的化学性质, 需对其化学相容性进行探究. 本工作首先制备出具有电荷转移等离激元共振特性的金-银纳米粒子, 其独特的双金属结构和良好的胶体稳定性不仅方便其DNA功能化和可编程自组装, 同时也有利于对金粒子表面沉积的银纳米粒子尺寸和形貌变化进行观测. 基于Au-Ag纳米粒子与金纳米粒子的简单混合和组装实验, 清楚揭示了金纳米粒子增强的银刻蚀现象, 并提出金表面促进银转移反应(GSPSTR)这一化学机制, 以及增强银和金纳米单元间化学相容性的有效办法. 本工作对于利用DNA导向组装实现银纳米粒子参与的多元金属异质结构, 以及发展等离激元和催化等功能与应用具有重要意义, 更为正确理解金属银参与的纳米合成与组装等过程提供了新认识.

关键词: 金纳米粒子, 银纳米粒子, 等离激元, 异质组装, 化学相容性

Metal nanoparticles displaying localized surface plasmon resonance (LSPR) are attractive to sensing, biological imaging, and nanomedical applications. Building nanoassemblies of different metals is of great value toward heterogeneous plasmon hybridization, LSPR tuning, and “lighting-up” of dark LSPR states. Based on the distinct activities of different nanounits and their spatial proximity, functional synergy or relay may be realized. Gold and silver nanomaterials strongly absorb and scatter light in the visible region, making them first choices for plasmonic engineering. However, silver is far less popular than gold in the bottom-up construction of plasmonic structures, which is mainly due to its unsatisfactory chemical and colloidal stabilities. On the other hand, the interband transition of silver nanoparticles is far away from their plasmon resonance, which, along with their relatively small plasmon loss, leads to strong and somewhat symmetric LSPR peaks superior to gold nanoparticles. More importantly, the simultaneous introduction of gold and silver into self-assembled structures is expected to generate properties and functions that cannot be realized by homogeneous assemblies. However, the dramatically different chemical properties of gold and silver might lead to a compatibility problem. To address this issue, Au-Ag heterodimeric nanoparticles featuring a charge transfer plasmon resonance are synthesized and utilized as ideal silver-containing materials to uncover the Au-Ag chemical incompatibility. The good colloidal stability of the Au-Ag nanoparticles enables their DNA grafting and DNA-programmable assembly. In addition, the bimetallic nature and the charge transfer plasmon resonance of the Au-Ag nanoparticles facilitate the observation of a silver etching reaction in the presence of gold nanoparticles. The chemical source of such an incompatibility is then proposed, which involves several “solid-solution-solid” pathways capable of promoting a “silver-transfer” to the gold surface. Such understanding finally leads to strategies toward improved gold-silver chemical compatibility. This work paves a way to the construction of heterogeneous nanoassemblies involving silver and other noble metals toward sensing, catalysis, light harvesting, and optoelectronics.

Key words: gold nanoparticle, silver nanoparticle, plasmon, heteroassembly, chemical compatibility

引用此文

王程鋆, 王悦靓, 王会巧, 邓兆祥. 金-银纳米异质组装过程的化学不相容性[J]. 化学学报, 2024, 82(7): 763-771.

Chengjun Wang, Yueliang Wang, Huiqiao Wang, Zhaoxiang Deng. Unveiling the Chemical Incompatibility of Au-Ag Heteronanoassembly[J]. Acta Chimica Sinica, 2024, 82(7): 763-771.

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图/表 7

图1. 金表面促进银蚀刻溶出-液相迁移-异相沉积过程的示意图

Figure 1. Gold surface-promoted silver stripping followed by solution transport and on-gold deposition of the leached silver species

图2. 金-银双金属异质纳米粒子(Au-AgNP)的合成与表征. (a)合成过程示意图. (b, c)经不同反应时长所得产物的琼脂糖凝胶电泳图(b)和TEM图像(c). (d)金-银异质结构的扫描透射电镜(STEM)图像和基于能量色散X射线谱(EDX)的元素分布图. (e)不同反应时间对应产物的消光谱

Figure 2. Synthesis and characterizations of Au-Ag bimetallic heterogeneous nanoparticles (Au-AgNPs). (a) Schematic illustration of the synthesis process of Au-AgNPs. (b, c) Agarose gel electrophoresis (b) and TEM imaging (c) of as-formed Au-AgNPs at different reaction durations. (d) STEM imaging and EDX mapping of an Au-AgNP. (e) Extinction spectra of the Au-AgNPs obtained at different reaction durations

图3. Au-AgNP的DNA功能化及DNA导向核-卫星自组装. (a)不同DNA修饰密度下Au-AgNP的琼脂糖凝胶电泳图. (b)高密度DNA修饰的Au-AgNP电镜图像. (c~f) ssDNA多功能化Au-AgNP与ssDNAc单功能化的5 nm AuNP (c, d)、15 nm AuNP (e)和PtNP (f)在25 ℃ (c, e, f)和37 ℃ (d)下杂交形成的核-卫星结构TEM图像. 内插图为高倍TEM图像. (g)组装产物的琼脂糖凝胶电泳分离. 实线框代表组装产物, 虚线框指示未组装的Au-AgNP(DNA不互补, TEM证据见支持信息图S5)

Figure 3. DNA conjugation of Au-AgNPs and their DNA-guided assembly into core-satellites. (a) Agarose gel electropherogram of Au-AgNPs featuring different DNA grafting densities. (b) A typical TEM image of Au-AgNPs bearing high-density DNA grafts. (c~f) TEM images of as-formed core-satellite assemblies upon hybridization of ssDNA-multifunctionalized Au-AgNPs with ssDNAc-monoconjugated 5 nm (c, d) and 15 nm (e) AuNPs, as well as PtNPs (f) at 25 ℃ (c, e, f) and 37 ℃ (d), respectively. Insets are high-magnification TEM images. (g) Agarose gel electrophoreses of assembly products. Solid boxes show hybridization products, and dashed boxes mark unassembled Au-AgNPs due to DNA non-complementarity (see Figure S5 for TEM evidences)

图4. Au-AgNP与带有不同表面配体的AuNP混合作用后蚀刻情况表征. (a)分别将BSPP和柠檬酸根保护的30 nm AuNP以1∶1 (i, iii)和10∶1 (ii, iv)粒子数比与Au-AgNP混合并在常温下作用2 h后, 通过琼脂糖凝胶电泳对混合物中的Au-AgNP进行分离, 混合前和混合后的样品均在胶图中呈现. (b)与AuNP作用后所得Au-AgNP样品(编号为i~iv)的TEM图像(样品经电泳分离). 内插图为对应结构的高倍TEM图像. 值得注意的是, BSPP保护的AuNP(Au-BSPP)与Au-AgNP作用后滞留在凝胶加样孔中, 这是因为银的沉积降低了其胶体稳定性; 柠檬酸根保护的AuNP(Au-Cit)本身胶体稳定性较差, 与Au-AgNP作用后同样滞留在加样孔内. 当提高AuNP比例后, Au-AgNP对应的电泳条带由棕绿色(i, iii)变为紫红色(ii, iv), 表明银组分发生明显流失, 这与电镜观测结果相符

Figure 4. Silver etching of Au-AgNPs upon mixing with AuNPs bearing different surface ligands. (a) BSPP or citrate-capped 30 nm AuNPs were mixed with Au-AgNPs at 1∶1 (i, iii) and 10∶1 (ii, iv) molar ratios, and the mixtures were incubated at room temperature for 2 h. Au-AgNPs in the mixtures were analyzed by agarose gel electrophoresis. Samples before and after mixing were examined in the gel. (b) TEM images of gel-isolated Au-AgNPs after interacting with AuNPs (labeled i~iv). Insets show high-magnification TEM images of the corresponding structures. Note that BSPP-protected AuNPs (Au-BSPP) remained trapped in the gel loading wells after reacting with Au-AgNPs, indicating reduced colloidal stability due to silver deposition. The citrate-capped AuNPs also aggregated in the gel wells due to their inherent colloidal instability. At an increased AuNP:Au-AgNP molar ratio of 10∶1, the color of the Au-AgNP bands changed from brown-green (i, iii) to purple-red (ii, iv), indicating significant silver loss consistent with TEM evidences

Metal content	R₁	R₂	S	Total
m_Au/μg	2.928	7.014	0.162	10.104
m_Ag/μg	0.492	0.978	0.012	1.482

表1. Au-AgNP与5 nm AuNP按1∶2000粒子数比在纯水中混合, 室温下作用12 h后, 经低速(1940 g)和高速(21500 g)两次离心, 所得沉淀(记作R1和R2, 分别对应两次离心)和最终上清液(S)中金和银的质量含量

Table 1. Mass contents of gold and silver elements in the precipitates after low (1940 g) and high (21500 g) speed centrifugations (marked as R1 and R2, respectively) and the final supernatant (labelled as S) of a mixture containing Au-AgNPs and 5 nm AuNPs (combined in water) at a molar ratio of 1∶2000 upon incubation at room temperature for 12 h

图5. 以30 nm AuNP为种子合成的Au-AgNP与5 nm AuNP按1∶300粒子数比室温混合作用10 h后的表征结果. (a)相应样品的琼脂糖凝胶电泳图. Au5和Au30分别代表5 nm和30 nm AuNP. (b, c)混合物经电泳分离后不同条带(1~3)对应样品的消光光谱(b)和TEM图像(c). (d)条带1对应样品的STEM图像(d1)和EDX元素分布图(d2~d4)

Figure 5. Characterizations of the mixture between 30 nm AuNP-seeded Au-AgNPs and 5 nm AuNPs at a 1∶300 molar ratio after being incubated at room temperature for 10 h. (a) Agarose gel electrophoresis of the corresponding samples. Au5 and Au30 represent 5 nm and 30 nm AuNPs, respectively. (b, c) Extinction spectra (b) and TEM images (c) of the samples extracted from bands 1~3 marked in (a). (d) STEM imaging (d1) and EDX mapping (d2~d4) of the gel-isolated sample labelled as band 1

图6. 利用巯基PEG(化学式为HSCH2CH2(OCH2CH2)8COOH)的表面钝化作用抑制Au-AgNP和AuNP发生核-卫星组装时的银蚀刻现象. (a)经不同分子表面修饰后的Au-AgNP和5 nm AuNP混合前、后的消光光谱变化. (b)经不同分子表面修饰后的Au-AgNP和5 nm AuNP混合作用前、后, 通过TEM测量所得Au-AgNP中银区和金区的宽度比. 误差棒代表测量结果的高斯分布标准差(σ). (c)相应样品的琼脂糖凝胶电泳分离图. (d)与(a~c)中标记i~viii对应样品的TEM图像. 内插图为对应结构的高倍电镜图像

Figure 6. Suppressed silver etching upon surface passivation by thiolated PEG (HSCH2CH2(OCH2CH2)8COOH) during core-satellite assembly of Au-AgNPs and 5 nm AuNPs. (a) Extinction spectra of Au-AgNPs and 5 nm AuNPs (capped by different molecules) recorded before and after mixing them together for prolonged interactions. (b) TEM-measured width ratios between silver and gold domains in Au-AgNPs before and after their interaction with 5 nm AuNPs. The nanoparticles were capped by different molecules. Error bars represent standard deviations (σ) of Gaussian fittings. (c) Agarose gel electrophoresis of various samples. (d) TEM images of gel-isolated Au-AgNPs and their core-satellite assemblies with 5 nm AuNPs, corresponding to labels i~viii in (a~c). Insets show high-magnification TEM images of corresponding structures

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