Discovery, Mechanism, and Application of Antigalvanic Reaction
- 1 November 2018
- journal article
- review article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 51 (11), 2774-2783
- https://doi.org/10.1021/acs.accounts.8b00374
Abstract
Among many outstanding findings associated with the quantum size effect, one of the most exciting is the discovery of the antigalvanic reaction (AGR), which is the opposite of the classic galvanic reaction (GR) that has a history of nearly 240 years. The GR, named after Italian scientist Luigi Galvani, involves the spontaneous reduction of a noble-metal cation by a less noble metal in solution driven by the difference in electrochemical potentials. Classic galvanic reduction has been widely applied and has recently received particular interest in nanoscience and nanotechnology. However, the opposite of GR, that is, reduction of metal ions by less reactive (or more noble) metals, has long been regarded as a virtual impossibility until the recent surprising findings regarding atomically precise ultrasmall metal nanoparticles (nanoclusters), which bridge the gap between metal atoms (complexes) and metal nanocrystals and provide opportunities for novel scientific findings due to their well-defined compositions and structures. The AGR is significant not only because it is the opposite of the classic galvanic theory but also because it opens extensive applications in a large range of fields, such as sensing and tuning the compositions, structures, and properties of nanostructures that are otherwise difficult to obtain. Starting with the proposal of the general AGR concept in 2012 by Wu, a new era began, in which AGR received widespread attention and was extensively studied. After years of effort, great advances have been achieved in the research on AGR, which will be reviewed below. In this Account, we first provide a short introduction to the AGR concept and then discuss the driving force of the AGR together with the effecting factors, including the ligand, particle size, solvent, metal ion precursor, and ion dose. Subsequently, the application of the AGR in engineering atomically precise alloy (bimetallic and trimetallic) and monometallic nanoclusters is described, and tuning the properties of the parent nanoclusters is also included. In particular, four alloying modes (namely, (i) addition, (ii) replacement, (iii) replacement and structural transformation, and (iv) nonreplacement and structural transformation) associated with the AGR are discussed. After that, the applications of the AGR in metal ion sensing and antioxidation are reviewed. Finally, future prospects are discussed, and some challenging issues are presented at the end of this Account. It is expected that this Account will stimulate more scientific and technological interests in the AGR, and exciting progress in the understanding and application of the AGR will be made in the coming years.Funding Information
- Hefei Institutes of Physical Science, Chinese Academy of Sciences (KP-2017-16)
- National Natural Science Foundation of China (51502299, 21222301, 21528303, 21701179, 21771186, 21829501)
- Natural Science Foundation of Anhui Province (1708085QB36)
This publication has 44 references indexed in Scilit:
- An Ultrafast Look at Au NanoclustersAccounts of Chemical Research, 2013
- Fluorescent Probes: Well-Defined Nanoclusters as Fluorescent Nanosensors: A Case Study on Au25(SG)18 (Small 13/2012)Small, 2012
- Quantum Sized Gold Nanoclusters with Atomic PrecisionAccounts of Chemical Research, 2012
- Well‐Defined Nanoclusters as Fluorescent Nanosensors: A Case Study on Au25(SG)18Small, 2012
- Anti‐Galvanic Reduction of Thiolate‐Protected Gold and Silver NanoparticlesAngewandte Chemie, 2012
- Engineering the properties of metal nanostructures via galvanic replacement reactionsMaterials Science and Engineering: R: Reports, 2010
- The Story of a Monodisperse Gold Nanoparticle: Au25L18Accounts of Chemical Research, 2010
- Reactivity of [Au25(SCH2CH2Ph)18]1−Nanoparticles with Metal IonsThe Journal of Physical Chemistry C, 2010
- Size dependent redox behavior of monolayer protected silver nanoparticles (2–7 nm) in aqueous mediumPhysical Chemistry Chemical Physics, 2004
- The work function of small metal particles and its relation to electrochemical propertiesSurface Science, 1985