Galvanic Replacement of Semiconducting CuTCNQF ₄ with Ag ⁺ Ions to Enhance Electron Transfer Reaction

Abstract

Inspired by the electroless galvanic replacement (GR) process where a spontaneous redox reaction occurs between two metal species primarily due to the difference in the standard electrode potential of the metal/metal ion couples, a facile strategy is developed to fabricate hybrid materials of metal organic semiconducting materials. The GR of CuTCNQF4, a metal organic charge transfer complex with Ag+ ion results in the formation of hybrids, wherein at low Ag+ ion concentrations, a hybrid of Ag nanoparticles decorated on the surface of CuTCNQF4 is obtained. In contrast, high Ag+ ion concentrations show the formation of AgTCNQF4/CuTCNQF4 hybrids with Ag nanoparticle decoration on the surface of the CuTCNQF4 structures. While the GR reaction results in different hybrids depending on the concentration of Ag+ ions and the availability of underlying Cu foil, we observe that the resulting hybrids have an influence on the catalytic and electrical properties. The outcomes presented in this work present a strong foundation for fabricating hybrid materials encompassing metal organic charge transfer complexes and exploring their properties for new biological, catalytic and electronic applications.

Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

“…The rich electrical, chemical, magnetic, and optoelectronic properties of charge-transfer complexes based on 7,7,8,8-tetracyanoquinodimethane (TCNQ) has seen substantial interest in using these materials for a range of applications ( Figure S1, Supplementary Materials show the chemical structure of TCNQ) [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 ]. The pioneering work led by Dunbar, Miller, Robson, and Bond have seen the development of several strategies including physical [ 9 , 10 ], photochemical [ 11 , 12 , 13 ], vapor deposition [ 9 , 14 , 15 ], electrochemical [ 5 , 13 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ], and wet-chemical synthesis methods [ 19 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ] for the fabrication of TCNQ-based charge transfer complexes. The resultant materials have been used as sensors [ 14 , 15 , 37 , 38 ], photocatalysts […”

“…The pioneering work led by Dunbar, Miller, Robson, and Bond have seen the development of several strategies including physical [ 9 , 10 ], photochemical [ 11 , 12 , 13 ], vapor deposition [ 9 , 14 , 15 ], electrochemical [ 5 , 13 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ], and wet-chemical synthesis methods [ 19 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ] for the fabrication of TCNQ-based charge transfer complexes. The resultant materials have been used as sensors [ 14 , 15 , 37 , 38 ], photocatalysts [ 19 , 23 , 24 , 25 , 26 , 29 , 30 , 31 , 32 , 33 , 35 , 36 ], data storage systems [ 39 ...…”

“…This is because, after the addition of fresh TCNQ 0 , the reaction would contain more of the TCNQ 0 species than TCNQ − species [ 34 ]. This approach resulted in structures of over 50 µm, which was previously limited to 10–15 µm through conventional wet-chemical synthesis [ 19 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ]. Furthermore, we proposed the use of a bisolvent mixture where a small fraction of water was mixed with TCNQ 0 dissolved in MeCN.…”

LSPR‐Induced Catalytic Enhancement Using Bimetallic Copper Fabrics Prepared by Galvanic Replacement Reactions

“…Multicomponent nanomaterials, such as bimetallic structures and composites continue to receive significant interest as they offer enhanced optical, physical and catalytic properties compared to their individual counterparts. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] In particular, nanostructures composed by two or more metals have shown great promise for applications in catalysis and sensing. To this end, a variety of solutionbased synthesis routes including co-reduction, [21][22][23] thermal decomposition, [24,25] microwave, [26,27] galvanic replacement, [8,[28][29][30] and seeded growth [23,31,32] have been employed to synthesize bimetallic nanomaterials.…”

“…[2,16] GR reactions are not only restricted to metallic systems and the concept is also extendable to inorganic [41] and organic semiconductors. [3,7,9,11,14,15] As such, this facile strategy has tremendous potential, as it is limited by no more than the requirement of a favourable difference in the reduction potentials of two reacting redox active species.…”