Unveiling the Chemical Incompatibility of Au-Ag Heteronanoassembly

doi:10.6023/A24040147

Abstract

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

Cite this article

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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Fig. & Tab. 7

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

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

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)

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

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

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

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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