Journal
CHEMICAL ENGINEERING JOURNAL
Volume 387, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2020.124129
Keywords
Metal nanoclusters; CO2 adsorption; CO2 -responsiveness; Photoluminescence; Hyperbranched polymers
Categories
Funding
- National Natural Science Foundation, China [21875159, 21976130]
- Tianjin Natural Science Foundation, China [18JCYBJC86800, 18JCYBJC23400]
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Stimuli-responsive metal nanoclusters (NCs) are intriguing materials due to their wide applications in photoluminescence (PL) sensors, bioimaging and catalysis. CO2 gas as a green stimulus could arouse the PL variation of certain metal NCs only under high-pressure condition. Metal NCs responding to the normal-pressure CO2 have not been reported yet. In this work, hydroxyl-terminated hyperbranched polyethylenimine (HPEI-OH) was used to mediate the preparation of water-soluble Au NC assemblies (Au NC-As) with crystallization-induced emission (CIE) nature. HPEI-OH played a multifunctional role, such as reducing Au ions, endowing water solubility to Au NC-As, packing thiolated Au NCs closely and enabling CO2-responsiveness to Au NC-As. Controlling the preparation pH at 2.0 or 3.2, red or yellow-emitting Au NC-As with quantum yield of ca. 4.6% or 5.8% were achieved. The as-prepared CIE-type Au NC-As possessed pH-responsive characteristic and strong PL emission was achieved under acidic condition. The CIE nature rendered not only strong PL emission to Au NC-As, but also strong photoelectron emission verified by the X-ray photoelectron spectroscopy. The introduction of Zn2+ ions extended the application range of Au NC-As from acidic condition fill to weak basic condition. Under neutral condition, the formed complex of Zn2+/Au NC-As showed reversible PL response to the normal-pressure CO2/N-2 cycling through adsorption and desorption process. Finally, the application of the complex in measuring the CO2 concentration of carbonated beverages was presented.
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