Robust Nanostructured Silver and Copper Fabrics with Localized Surface Plasmon Resonance Property for Effective Visible Light Induced Reductive Catalysis

Anderson, Samuel R.; Mohammadtaheri, Mahsa; Kumar, Dipesh; O’Mullane, Anthony P.; Field, Matthew R.; Ramanathan, Rajesh; Bansal, Vipul

doi:10.1002/admi.201500632

Cited by 49 publications

(40 citation statements)

References 48 publications

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“…The organic semiconductor AgTCNQ, on the other hand, has a narrow bandgap ( Eg = 0.48 eV) with a work function of 5.17 eV, as recently determined through our in‐depth studies on Ag/AgTCNQ interfaces . The metallic Ag sandwiched between these two semiconductors has a work function of 4.7 eV . Our recent study has shown that Ag and AgTCNQ have appropriate band structures to facilitate rapid electron transfer from Ag to AgTCNQ at the Ag/AgTCNQ interface under photoexcitation conditions .…”

Section: Resultssupporting

confidence: 59%

Long‐Range Ordered Crystals of 3D Inorganic–Organic Heterojunctions via Colloidal Lithography

et al. 2019

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Colloidal lithography (CL) has evolved as an alternative to conventional photo‐ and electron‐beam lithography to pattern surfaces with nanometer range resolution. As CL offers substrate‐independent precise positioning and patterning of nanomaterials as long‐range ordered crystals, this has seen new opportunities in optoelectronics. Herein, the scope of CL is expanded to fabricate for the first time, 3D organic–inorganic heterojunction photocatalysts with well‐controlled spacing and coverage density. To achieve this, monodisperse polystyrene (PS) beads of different sizes are used as colloidal masks on a ZnO substrate. Electron beam assisted silver deposition onto these PS masks, and subsequent removal of PS lead to the formation of patterns of silver nanostars on the ZnO thin film. The solid–vapor reaction of silver nanostars with a metal‐coordinating charge‐transfer complex of 7,7,8,8‐tetracyanoquinodimethane (TCNQ) allows spontaneous conversion of Ag nanostars to the large aspect ratio nanowires of metal–organic AgTCNQ semiconductors. This strategy, combining the strengths of CL with high electron affinity of TCNQ molecules allows facile fabrication of long‐range patterns of the heterojunctions of organic (AgTCNQ) and inorganic (ZnO) semiconductors. These surface‐supported 3D heterojunctions act as outstanding photocatalysts through their ability to efficiently separate the electron–hole pairs and thus increasing the electron–hole life times.

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Section: Resultssupporting

confidence: 59%

Long‐Range Ordered Crystals of 3D Inorganic–Organic Heterojunctions via Colloidal Lithography

et al. 2019

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“…The introduction of increasing amounts of water during CuTCNQ synthesis in MeCN consistently improves the catalytic performance of obtained catalysts ( Table 2 ). Metallic Cu is known to be an outstanding catalyst for ferricyanide reduction reaction, and Cu foil took 22.5 min to drive the reaction to 95% completion. This activity of metallic Cu is better than the CuTCNQ catalyst grown using conventional route in 100% MeCN that took 38 min.…”

Section: Resultsmentioning

confidence: 99%

Role of Water in the Dynamic Crystallization of CuTCNQ for Enhanced Redox Catalysis (TCNQ = Tetracyanoquinodimethane)

Siu

Anderson

Mohammadtaheri

et al. 2017

Adv Materials Inter

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have established a breadth of TCNQ-based charge-transfer complexes, each with unique properties. While growing recognition of TCNQ-based materials has led to a number of fabrication strategies including electrochemical, vapor deposition, and wet chemical routes; the applicability of these materials has until recently been severely restricted to electronics. [21][22][23][24][25][26] A unique subset of this group of materials is MTCNQ ionic charge transfer complexes, wherein M corresponds to a transition metal cation (CuTCNQ and AgTCNQ are the most extensively studied) and TCNQ is an anion. [1][2][3][4][5][6][7][8] The presence of transition metal in these metal-organic charge transfer complexes offers a unique opportunity to combine their inherent organic semiconducting properties with the well-established applications of metals in catalysis, sensing, and biology. In recent years, our group and others have shown the potential of these materials beyond electronics, such that CuTCNQ and its metal composites were found as outstanding catalysts for electron transfer and dye degradation reactions; [1][2][3]5] CuTCNQ/ZnO heterojunctions as a humidity sensor; [27] CuTCNQ nanoarrays as pressure sensors; [28] KTCNQ, NaTCNQ, and LiTCNQ as highly specific NO x /H 2 gas sensors; [29,30] and AgTCNQ as antimicrobial agents. [31] These emerging applications of MTCNQ materials now warrant new developments in the current fabrication strategies such that obtained materials are best suited for the targeted application.For CuTCNQ, the current wet chemical fabrication strategy employs a Cu foil (Cu 0 ) as a source of metal, which is immersed in a TCNQ 0 solution dissolved in acetonitrile (MeCN). [1][2][3]32] A spontaneous redox reaction leads to crystallization of phase I CuTCNQ [i.e., Cu + TCNQ − ] microrods vertically aligned on the surface of the Cu foil. [21] A limitation of this approach is that the length of the CuTCNQ microrods is typically restricted to ≈10-15 µm. This is primarily because the as-synthesized CuTCNQ concomitantly dissolves into Cu + and TCNQ − ions on prolonged exposure to MeCN. [32] The concurrent dissolution/ crystallization of CuTCNQ does not allow the growth of these materials beyond certain dimensions. [32] In addition to dissolution, a physicochemical change occurs through which the original conductive phase I CuTCNQ (4.8 × 10 −3 S cm −1 ) transforms A new bisolvent approach is introduced to overcome the limitation of wet chemical routes of a semiconducting phase I CuTCNQ (7,7,8,8-tetracyanoquinodimethane) synthesis, which currently does not allow these materials to be grown beyond certain dimensions (10-15 µm). The use of water as a cosolvent during acetonitrile-mediated conventional synthesis of CuTCNQ allows a dynamic control over its crystallization and dissolution process through favorably shifting the reaction equilibrium. This enables CuTCNQ structures of unique morphologies with secondary growth, alongside dimensions exceeding 100 µm to be produced. These new morphologies of phase I CuTCNQ show re...

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“…Similar to pristine CuTCNQF 4 , the Cu 2p core level spectra obtained from the materials after galvanic replacement with 1 μM, 100 μM and 1 mM Ag + ions show characteristic 2p 3/2 and 2p 1/2 splitting components from the Cu + species (Figure a ‐ ii‐iv). The absence of signatures corresponding to the shake‐up satellites between 940–950 eV suggests that the GR process does not lead to the formation of Cu 2+ species typically seen in CuO or Cu(OH) 2 ,. This observation is different from our previous work where the GR reaction between CuTCNQ and Ag + resulted in the formation of Cu 2+ species, suggesting that the GR process of CuTCNQF 4 with Ag + does not allow the formation of Cu 2+ species.…”

Section: Resultsmentioning

confidence: 99%

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

Ramanathan

Kumar

et al. 2017

ChemistrySelect

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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.

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Robust Nanostructured Silver and Copper Fabrics with Localized Surface Plasmon Resonance Property for Effective Visible Light Induced Reductive Catalysis

Cited by 49 publications

References 48 publications

Long‐Range Ordered Crystals of 3D Inorganic–Organic Heterojunctions via Colloidal Lithography

Long‐Range Ordered Crystals of 3D Inorganic–Organic Heterojunctions via Colloidal Lithography

Role of Water in the Dynamic Crystallization of CuTCNQ for Enhanced Redox Catalysis (TCNQ = Tetracyanoquinodimethane)

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

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Robust Nanostructured Silver and Copper Fabrics with Localized Surface Plasmon Resonance Property for Effective Visible Light Induced Reductive Catalysis

Cited by 49 publications

References 48 publications

Long‐Range Ordered Crystals of 3D Inorganic–Organic Heterojunctions via Colloidal Lithography

Long‐Range Ordered Crystals of 3D Inorganic–Organic Heterojunctions via Colloidal Lithography

Role of Water in the Dynamic Crystallization of CuTCNQ for Enhanced Redox Catalysis (TCNQ = Tetracyanoquinodimethane)

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

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