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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Energy and Catalysis".

Deadline for manuscript submissions: closed (20 August 2023) | Viewed by 23685

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Dr. Palaniappan Subramanian

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Guest Editor

New Technologies-Research Center, University of West Bohemia, 30100 Plzen, Czech Republic
Interests: electrochemistry; nanocatalyst; nanomaterials for electrochemical energy devices; bifunctional electrochemical devices; power to chemicals and fuels; biosensors; chemosensors
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Dr. Kalim Deshmukh

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Guest Editor

New Technologies Research Center, University of West Bohemia, Univerzitní 8, 30614 Plzeň, Czech Republic
Interests: advanced polymer nanocomposites; synthesis and characterization; energy storage; sensors; EMI shielding applications
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Special Issue Information

Dear Colleagues,

Nanostructured materials composed of a single component do not often possess all the desired properties required for delivering optimal device-level performance outcomes in different areas of electrochemical science and technology. The development of nanostructured materials for lab-scale electrochemical energy devices involves the tuning of properties, such as the surface area, conductivity, active site density, chemical and electrochemical stability, and product selectivity. Nanomaterials developed for application in voltammetric devices involve the design of nanoarchitecture that can support the highly sensitive detection of target analytes such as toxic chemicals, biomarkers, and microorganisms with a high degree of accuracy. The advent of two-dimensional nanomaterials and their composites has opened an active area of research, where many of the desired material properties that are not fulfilled by single-component systems can be satisfactorily achieved by the optimal combination of the properties of several individual material components.

The design, synthesis, characterization of advanced materials including two-dimensional materials and their composites are highly diverse and vary depending on the targeted electrochemical application. This Special Issue aims to present the most recent advances and progress achieved in the discovery and development of advanced nanomaterials and nanocomposites for electrochemical applications. We welcome original research articles and review papers focused on the synthesis, unique properties and structure-property-perfromance relationships of advanced nanomaterials and nanocomposites developed for applications in electrochemical energy and bio/chemosensing devices.

Dr. Palaniappan Subramanian
Dr. Kalim Deshmukh
Guest Editors

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Keywords

2D metal-based nanocomposite
MXene-based materials
metal-organic framework-derived electrode materials
metal-organic framework graphene heterostructures
2D carbon nanocomposite
covalent organic framework-based nanocomposites
porous nanostructures
metallenes
cyanogel, aerogel and their nanocomposite derivatives
polymer nanocomposites
electrocatalyst for fuel cell and electrolyzers
supercapacitors
Li-ion, Na-ion, Li–O2, Zn-ion, Zn–air and redox flow battery applications
chemo- and biosensors

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Published Papers (8 papers)

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Research

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12 pages, 1609 KiB

Open AccessEditor’s ChoiceArticle

DNA-Templated Silver Nanoclusters as Dual-Mode Sensitive Probes for Self-Powered Biosensor Fueled by Glucose

by Akhilesh Kumar Gupta and Alexey V. Krasnoslobodtsev

Nanomaterials 2023, 13(8), 1299; https://doi.org/10.3390/nano13081299 - 7 Apr 2023

Cited by 17 | Viewed by 4726

Abstract

Nanomaterials have been extensively explored in developing sensors due to their unique properties, contributing to the development of reliable sensor designs with improved sensitivity and specificity. Herein, we propose the construction of a fluorescent/electrochemical dual-mode self-powered biosensor for advanced biosensing using DNA-templated silver nanoclusters (AgNCs@DNA). AgNC@DNA, due to its small size, exhibits advantageous characteristics as an optical probe. We investigated the sensing efficacy of AgNCs@DNA as a fluorescent probe for glucose detection. Fluorescence emitted by AgNCs@DNA served as the readout signal as a response to more H₂O₂ being generated by glucose oxidase for increasing glucose levels. The second readout signal of this dual-mode biosensor was utilized via the electrochemical route, where AgNCs served as charge mediators between the glucose oxidase (GOx) enzyme and carbon working electrode during the oxidation process of glucose catalyzed by GOx. The developed biosensor features low-level limits of detection (LODs), ~23 μM for optical and ~29 μM for electrochemical readout, which are much lower than the typical glucose concentrations found in body fluids, including blood, urine, tears, and sweat. The low LODs, simultaneous utilization of different readout strategies, and self-powered design demonstrated in this study open new prospects for developing next-generation biosensor devices. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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17 pages, 4800 KiB

Open AccessArticle

Synthesis of Platinum Nanocrystals Dispersed on Nitrogen-Doped Hierarchically Porous Carbon with Enhanced Oxygen Reduction Reaction Activity and Durability

by Min Li, Feng Liu, Supeng Pei, Zongshang Zhou, Kai Niu, Jianbo Wu and Yongming Zhang

Nanomaterials 2023, 13(3), 444; https://doi.org/10.3390/nano13030444 - 21 Jan 2023

Cited by 7 | Viewed by 2596

Abstract

Platinum-based catalysts are widely used for efficient catalysis of the acidic oxygen reduction reaction (ORR). However, the agglomeration and leaching of metallic Pt nanoparticles limit the catalytic activity and durability of the catalysts and restrict their large-scale commercialization. Therefore, this study aimed to achieve a uniform distribution and strong anchoring of Pt nanoparticles on a carbon support and improve the ORR activity and durability of proton-exchange membrane fuel cells. Herein, we report on the facile one-pot synthesis of a novel ORR catalyst using metal–nitrogen–carbon (M–N–C) bonding, which is formed in situ during the ion exchange and pyrolysis processes. An ion-exchange resin was used as the carbon source containing R-N⁺(CH₃)₃ groups, which coordinate with PtCl₆²⁻ to form nanosized Pt clusters confined within the macroporous framework. After pyrolysis, strong M-N-C bonds were formed, thereby preventing the leaching and aggregation of Pt nanoparticles. The as-synthesized Pt supported on the N-doped hierarchically porous carbon catalyst (Pt/NHPC-800) showed high specific activity (0.3 mA cm⁻²) and mass activity (0.165 A mg_Pt⁻¹), which are approximately 2.7 and 1.5 times higher than those of commercial Pt/C, respectively. The electrochemical surface area of Pt/NHPC-800 remained unchanged (~1% loss) after an accelerated durability test of 10,000 cycles. The mass activity loss after ADT of Pt/NHPC-800 was 18%, which is considerably lower than that of commercial Pt/C (43%). Thus, a novel ORR catalyst with highly accessible and homogeneously dispersed Pt-N-C sites, high activity, and durability was successfully prepared via one-pot synthesis. This facile and scalable synthesis strategy for high-efficiency catalysts guides the further synthesis of commercially available ORR catalysts. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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10 pages, 3018 KiB

Open AccessCommunication

Facile Gram-Scale Synthesis of Co₃O₄ Nanocrystal from Spent Lithium Ion Batteries and Its Electrocatalytic Application toward Oxygen Evolution Reaction

by Jaegon Kim, Ho-Geun Kim, Hyun-Su Kim, Cu Dang Van, Min Hyung Lee and Ki-Wan Jeon

Nanomaterials 2023, 13(1), 125; https://doi.org/10.3390/nano13010125 - 26 Dec 2022

Cited by 6 | Viewed by 2319

Abstract

In this study, we demonstrate a new approach to easily prepare spinel Co₃O₄ nanoparticles (s-Co₃O₄ NPs) in the gram-scale from the cathode of spent lithium ion batteries (SLIBs) by the alkali leaching of hexaamminecobalt(III) complex ions. As-obtained intermediate and final products were characterized with powder X-ray diffraction (PXRD), Ultraviolet-Visible (UV–Vis), Fourier transform infrared (FTIR), and Transmission electron microscopy (TEM). Additionally, the synthesized s-Co₃O₄ NPs showed better electrocatalytic properties toward the oxygen evolution reaction (OER) in comparison to previously reported Co₃O₄ NPs and nanowires, which could be due to the more exposed electrocatalytic active sites on the s-Co₃O₄ NPs. Moreover, the electrocatalytic activity of the s-Co₃O₄ NPs was comparable to the previously reported RuO₂ catalysts. By taking advantage of the proposed recycling route, we would expect that various valuable transition metal oxide NPs could be prepared from SLIBs. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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13 pages, 3709 KiB

Open AccessArticle

An Improved Experiment for Measuring Lithium Concentration-Dependent Material Properties of Graphite Composite Electrodes

by Huibing Liu, Guoxing Zhang, Dawei Li and Junqian Zhang

Nanomaterials 2022, 12(24), 4448; https://doi.org/10.3390/nano12244448 - 14 Dec 2022

Cited by 4 | Viewed by 2274

Abstract

The in situ curvature measurement of bilayer beam electrodes is widely used to measure the lithium concentration-dependent material properties of lithium-ion battery electrodes, and further understand the mechano–electrochemical coupling behaviors during electrochemical cycling. The application of this method relies on the basic assumption that lithium is uniformly distributed along the length and thickness of the curved active composite layer. However, when the electrode undergoes large bending deformation, the distribution of lithium concentration in the electrolyte and active composite layer challenges the reliability of the experimental measurements. In this paper, an improved experiment for simultaneously measuring the partial molar volume and the elastic modulus of the graphite composite electrode is proposed. The distance between the two electrodes in the optical electrochemical cell is designed and graphite composite electrodes with four different thickness ratios are measured. The quantitative experimental data indicate that the improved experiment can better satisfy the basic assumptions. The partial molar volume and the elastic modulus of the graphite composite electrode evolve nonlinearly with the increase of lithium concentration, which are related to the phase transition of graphite and also affected by the other components in the composite active layer. This improved experiment is valuable for the reliable characterization of the Li concentration-dependent material properties in commercial electrodes, and developing next-generation lithium batteries with more stable structures and longer lifetimes. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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15 pages, 3647 KiB

Open AccessArticle

Nano-Dimensional Carbon Nanosphere Supported Non-Precious Metal Oxide Composite: A Cathode Material for Sea Water Reduction

by Jayasmita Jana, Tran Van Phuc, Jin Suk Chung, Won Mook Choi and Seung Hyun Hur

Nanomaterials 2022, 12(23), 4348; https://doi.org/10.3390/nano12234348 - 6 Dec 2022

Cited by 13 | Viewed by 2340

Abstract

Generation of hydrogen fuel at cathode during the electrolysis of seawater can be economically beneficial considering the vast availability of the electrolyte although it faces sluggishness caused by the anode reactions. In this regard a carbon nanosphere-protected CuO/Co₃O₄ (CCuU) composite was synthesized through heat treatment and was used as the cathode material for electrocatalytic seawater splitting. CCuU showed a significantly low overpotential of 73 mV@10 mA cm⁻², Tafel slope of 58 mV dec⁻¹ and relatively constant activity and morphology over a long time electrocatalytic study. A synergy within metal oxide centers was observed that boosted the proton-electron transfer at the active site. Moreover, the presence of carbon support increased the electroactive surface area and stability of the composite. The activity of the CCuU was studied for HER in KOH and alkaline NaCl solution to understand the activity. This work will pave the way for designing mesoporous non-precious electrocatalysts towards seawater electrocatalysis. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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16 pages, 5996 KiB

Open AccessArticle

Ni₂P Nanoparticle-Inserted Porous Layered NiO Hetero-Structured Nanosheets as a Durable Catalyst for the Electro-Oxidation of Urea

by Kun Ma, Hui Wang, Palanisamy Kannan and Palaniappan Subramanian

Nanomaterials 2022, 12(20), 3633; https://doi.org/10.3390/nano12203633 - 17 Oct 2022

Cited by 3 | Viewed by 2044

Abstract

The electro-oxidation of urea (EOU) is a remarkable but challenging sustainable technology, which largely needs a reduced electro-chemical potential, that demonstrates the ability to remove a notable harmful material from wastewater and/or transform the excretory product of humans into treasure. In this work, an Ni₂P-nanoparticle-integrated porous nickel oxide (NiO) hetero-structured nanosheet (Ni₂P@NiO/NiF) catalyst was synthesized through in situ acid etching and a gas-phase phosphating process. The as-synthesized Ni₂P@NiO/NiF catalyst sample was then used to enhance the electro-oxidation reaction of urea with a higher urea oxidation response (50 mA cm⁻² at 1.31 V vs. RHE) and low onset oxidation potential (1.31 V). The enhanced activity of the Ni₂P@NiO/NiF catalyst was mainly attributed to effective electron transport after Ni₂P nanoparticle insertion through a substantial improvement in active sites due to a larger electrochemical surface area, and a faster diffusion of ions occurred via the interactive sites at the interface of Ni₂P and NiO; thus, the structural reliability was retained, which was further evidenced by the low charge transfer resistance. Further, the Ni₂P nanoparticle insertion process into the NiO hetero-structured nanosheets effectively enabled a synergetic effect when compared to the counter of the Ni₂P/NiF and NiO/NiF catalysts. Finally, we demonstrate that the as-synthesized Ni₂P@NiO/NiF catalyst could be a promising electrode for the EOU in urea-rich wastewater and human urine samples for environmental safety management. Overall, the Ni₂P@NiO/NiF catalyst electrode combines the advantages of the Ni₂P catalyst, NiO nanosheet network, and NiF current collector for enhanced EOU performance, which is highly valuable in catalyst development for environmental safety applications. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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Review

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26 pages, 2121 KiB

Open AccessReview

Metal Recovery from Natural Saline Brines with an Electrochemical Ion Pumping Method Using Hexacyanoferrate Materials as Electrodes

by Sebastian Salazar-Avalos, Alvaro Soliz, Luis Cáceres, Sergio Conejeros, Iván Brito, Edelmira Galvez and Felipe M. Galleguillos Madrid

Nanomaterials 2023, 13(18), 2557; https://doi.org/10.3390/nano13182557 - 14 Sep 2023

Cited by 4 | Viewed by 2758

Abstract

The electrochemical ion pumping device is a promising alternative for the development of the industry of recovering metals from natural sources—such as seawater, geothermal water, well brine, or reverse osmosis brine—using electrochemical systems, which is considered a non-evaporative process. This technology is potentially used for metals like Li, Cu, Ca, Mg, Na, K, Sr, and others that are mostly obtained from natural brine sources through a combination of pumping, solar evaporation, and solvent extraction steps. As the future demand for metals for the electronic industry increases, new forms of marine mining processing alternatives are being implemented. Unfortunately, both land and marine mining, such as off-shore and deep sea types, have great potential for severe environmental disruption. In this context, a green alternative is the mixing entropy battery, which is a promising technique whereby the ions are captured from a saline natural source and released into a recovery solution with low ionic force using intercalation materials such as Prussian Blue Analogue (PBA) to store cations inside its crystal structure. This new technique, called “electrochemical ion pumping”, has been proposed for water desalination, lithium concentration, and blue energy recovery using the difference in salt concentration. The raw material for this technology is a saline solution containing ions of interest, such as seawater, natural brines, or industrial waste. In particular, six main ions of interest—Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, and SO₄²⁻—are found in seawater, and they constitute 99.5% of the world’s total dissolved salts. This manuscript provides relevant information about this new non-evaporative process for recovering metals from aqueous salty solutions using hexacianometals such as CuHCF, NiHCF, and CoHCF as electrodes, among others, for selective ion removal. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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33 pages, 10214 KiB

Open AccessReview

Recent Progress on Graphene-Based Nanocomposites for Electrochemical Sodium-Ion Storage

by Mai Li, Kailan Zhu, Hanxue Zhao and Zheyi Meng

Nanomaterials 2022, 12(16), 2837; https://doi.org/10.3390/nano12162837 - 18 Aug 2022

Cited by 6 | Viewed by 3379

Abstract

In advancing battery technologies, primary attention is paid to developing and optimizing low-cost electrode materials capable of fast reversible ion insertion and extraction with good cycling ability. Sodium-ion batteries stand out due to their inexpensive price and comparable operating principle to lithium-ion batteries. To achieve this target, various graphene-based nanocomposites fabricate strategies have been proposed to help realize the nanostructured electrode for high electrochemical performance sodium-ion batteries. In this review, the graphene-based nanocomposites were introduced according to the following main categories: graphene surface modification and doping, three-dimensional structured graphene, graphene coated on the surface of active materials, and the intercalation layer stacked graphene. Through one or more of the above strategies, graphene is compounded with active substances to prepare the nanocomposite electrode, which is applied as the anode or cathode to sodium-ion batteries. The recent research progress of graphene-based nanocomposites for SIBs is also summarized in this study based on the above categories, especially for nanocomposite fabricate methods, the structural characteristics of electrodes as well as the influence of graphene on the performance of the SIBs. In addition, the relevant mechanism is also within the scope of this discussion, such as synergistic effect of graphene with active substances, the insertion/deintercalation process of sodium ions in different kinds of nanocomposites, and electrochemical reaction mechanism in the energy storage. At the end of this study, a series of strategies are summarized to address the challenges of graphene-based nanocomposites and several critical research prospects of SIBs that provide insights for future investigations. Full article

(This article belongs to the Special Issue Advanced Nanomaterials and Nanocomposites for Electrochemical Applications)

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