Precisely Constructed Silver Active Sites in Gold Nanoclusters for Chemical Fixation of CO₂

Abstract

Precise control of the composition and structure of active sites in an atom‐by‐atom fashion remains insuperable for heterogeneous catalysts. Here, we introduce tailor‐made catalytic sites for the cycloaddition of CO2 to epoxides achieved by implementing Ag atoms at different levels of liberation in atomically precise Au nanoclusters. Our results reveal that a single open Ag site on the Au19Ag4 cluster improves the ring‐opening of epoxides and sequent CO2 insertion, while the partially exposed Ag site on the Au20Ag1 cluster exhibits a weak affinity for epoxides and poor efficiency for CO2 capture. Structural tunability imparted by the atom‐by‐atom tailoring and unusual atomic charges distributed on Au and Ag atoms of the three clusters seem to be crucial for promoting challenging bond cleavages and formations in the chemical utilization of CO2.

Stepwise assembly and reversible structural transformation of ligated titanium coated bismuth-oxo cores: shell morphology engineering for enhanced chemical fixation of CO2

“…It was reported that the conversion of epoxides into cyclic carbonates could be effectively improved by increasing the reaction temperature and pressure or prolonging the reaction time. [44][45][46][47] Indeed, although carried out under room temperature and 1 atm pressure, the yields of propylene carbonate and 1,2butylene carbonate by PTC-285 could still be increased to 99% and 95% by prolonging the reaction time to 48 hours (Table 3, entry 1, 3). In addition, the size effect of the substrate was investigated.…”

Physical Origin of Dual-Emission of Au–Ag Bimetallic Nanoclusters

“…Quantum-sized metal nanoclusters, which bridge the gap between organometallics and nanocrystals, exhibit dramatically unique electronic and optical properties, such as molecule-like energy gaps (Schaaff et al, 1997;Lee et al, 2004;Negishi et al, 2005;Walter et al, 2008;Zhu et al, 2008;Russier-Antoine et al, 2014;Bertorelle et al, 2017;Chakraborty and Pradeep, 2017), intense photoluminescence (Zheng et al, 2004;Zheng et al, 2007;Xie et al, 2009;Luo et al, 2012;Musnier et al, 2019) and catalytic properties (Tsunoyama et al, 2009;Zhu et al, 2010;Li et al, 2016a;Cai et al, 2019;Lv et al, 2019;Lv et al, 2020a;Yang et al, 2020a;Lv et al, 2020b;Cai et al, 2020;Li et al, 2021). Luminescent thiolated-protected Au and Ag NCs in particular have attracted tremendous interest due to their wide applications in bio-imaging, bio-medicine, sensing, and catalysis (Jin, 2010;Díez and Ras, 2011;Bonacic-Koutecky et al, 2012;Zheng et al, 2012;Luo et al, 2014;Sun and Jin, 2014;Jin et al, 2016;Lei et al, 2018;Yan et al, 2018;Ungor et al, 2021).…”

Total Structure of Bimetallic Core–Shell [Au42Cd40(SR)52]2− Nanocluster and Its Implications

“…There have been reports of incorporating different heterometals into gold NCs [3, 6–10] . These bimetallic NCs are also applied in bio‐sensing and catalysis with significantly enhanced functionalities [2, 11–17] …”

“…[3,[6][7][8][9][10] These bimetallic NCs are also applied in bio-sensing and catalysis with significantly enhanced functionalities. [2,[11][12][13][14][15][16][17] In thiolate-protected gold-based bimetallic NCs, a general trend of the distribution of metal elements is that the surface is typically composed of the less noble metal with low valence state, such as Ag I and Cu I , resembling Au I in homo gold NCs. [8,18,19] Heterometals with high valence state (II or higher), such as Cd, can be doped into the sub-surface (beneath the staple motifs) of thiolated gold NCs but only with a limited number of Cd atoms (e.g.…”