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Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions

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A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Electrocatalysis".

Deadline for manuscript submissions: closed (30 September 2018) | Viewed by 68554

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Special Issue Editors

Prof. Dr. Nicolas Alonso-Vante

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Guest Editor

IC2MP-UMR CNRS 7285, University of Poitiers, 86022 Poitiers, France
Interests: electrochemistry; photoelectrochemistry; ORR-, HER-, OER-electrocatalysis; energy and fuels; nanomaterials; micro-fuel cells
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Yongjun Feng

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Guest Editor

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology (BUCT), No. 15, Beisanhuan East Road, Chaoyang District, Beijing 100029, China
Interests: non-platinum metal electrocatalysts; oxygen reduction reaction (ORR); oxygen evolution reaction (OER); multifunctional layered nanomaterials; layered double hydroxides (LDHs); high-performance adsorption materials; removal of heavy metals and phosphate
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Hui Yang

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Guest Editor

Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai Pudong New Area, Haike Road No. 99, Shanghai 201210, China
Interests: Pt-based electrocatalysts for fuel cells’ reaction non-precious metal catalyst for hydrogen oxidation and oxygen reduction reactions; new proton exchange membrane with high stability; direct methanol fuel cells; energy storage materials

Special Issue Information

Dear Colleagues,

Increasing inevitable global demands for energy have stimulated considerable research on alternative energy harvesting technologies, conversion and storage systems with high efficiency, cost-effective and environmentally friendly systems, such as fuel cells, rechargeable metal-air batteries, unitized regenerative cells, and water electrolyzers. In these devices, the conversion between oxygen and water plays a key step in the development of oxygen electrodes: Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). To date, the state-of-art catalysts for ORR consist of platinum-based materials (Pt), while ruthenium (Ru)- and iridium (Ir)-oxides are the best-known OER catalyst materials. The scarcity of precious metals, their prohibitive cost, and declining activity greatly hamper the practice for large-scale applications. It is of paramount practical importance and interest to develop efficient and stable materials for the oxygen electrode, based on Earth-abundant non-noble metals. With the fast development of advanced nanotechnology, novel non-precious metal electrocatalysts for the oxygen reactions have been explored based on the innovative design in chemical compositions, structure, and morphology, and supports.

This Special Issue aims to cover recent progress and advances in novel non-precious metal electrocatalysts tailoring with high activity and stablity for the catalytic conversion between water and oxygen. Additionally, electrocatalytic activity, selectivity, durability, and mechanism for single or bifunctional oxygen electrode reactions should be important subjects for this Special Issue.

Prof. Dr. Nicolas Alonso-Vante
Prof. Dr. Yongjun Feng
Prof. Dr. Hui Yang
Guest Editors

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Keywords

Non-precious metal electrocatalysts
oxygen reduction reaction
oxygen evolution reaction
bifunctional electrocatalysts
electrocatalytic activity
electrocatalytic selectivity
electrocatalytic durability, unitizes fuel cells.

Published Papers (11 papers)

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Editorial

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3 pages, 169 KiB

Open AccessEditorial

Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions

by Nicolas Alonso-Vante, Yongjun Feng and Hui Yang

Catalysts 2019, 9(9), 731; https://doi.org/10.3390/catal9090731 - 29 Aug 2019

Cited by 7 | Viewed by 2041

Abstract

The collection of articles in the Catalyst special issue entitled “Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions” mirrors the relevance and strengths to address the inevitable increasing demand of energy [...] Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

Research

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11 pages, 2094 KiB

Open AccessArticle

Engineering Mesoporous NiO with Enriched Electrophilic Ni³⁺ and O⁻ toward Efficient Oxygen Evolution

by Xiu Liu, Zhi-Yuan Zhai, Zhou Chen, Li-Zhong Zhang, Xiu-Feng Zhao, Feng-Zhan Si and Jian-Hui Li

Catalysts 2018, 8(8), 310; https://doi.org/10.3390/catal8080310 - 30 Jul 2018

Cited by 25 | Viewed by 5470

Abstract

Tremendous efforts have been devoted to develop low-cost and highly active electrocatalysts for oxygen evolution reaction (OER). Here, we report the synthesis of mesoporous nickel oxide by the template method and its application in the title reaction. The as-prepared mesoporous NiO possesses a large surface area, uniform mesopores, and rich surface electrophilic Ni³⁺ and O⁻ species. The overpotential of meso-NiO in alkaline medium is 132 mV at 10 mA cm⁻¹ and 410 mV at 50 mA cm⁻¹, which is much smaller than that of the other types of NiO samples. The improvement in the OER activity can be ascribed to the synergy of the large surface area and uniform mesopores for better mass transfer and high density of Ni³⁺ and O⁻ species favoring the nucleophilic attack by OH⁻ to form a NiOOH intermediate. The reaction process and the role of electrophilic Ni³⁺ and O⁻ were discussed in detail. This results are more conducive to the electrochemical decomposition of water to produce hydrogen fuel as a clean and renewable energy. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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11 pages, 2799 KiB

Open AccessArticle

Cobalt and Nitrogen Co-Doped Graphene-Carbon Nanotube Aerogel as an Efficient Bifunctional Electrocatalyst for Oxygen Reduction and Evolution Reactions

by Xiaochang Qiao, Jutao Jin, Hongbo Fan, Lifeng Cui, Shan Ji, Yingwei Li and Shijun Liao

Catalysts 2018, 8(7), 275; https://doi.org/10.3390/catal8070275 - 07 Jul 2018

Cited by 24 | Viewed by 5719

Abstract

In this study, a low-cost and environmentally friendly method is developed to synthesize cobalt and nitrogen co-doped graphene-carbon nanotube aerogel (Co-N-GCA) as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The as-prepared Co-N-GCA has a hierarchical meso- and macroporous structure with a high N doping level (8.92 at. %) and a large specific surface area (456 m² g⁻¹). In an alkaline medium, the catalyst exhibits superior ORR electrocatalytic activity with an onset potential 15 mV more positive than Pt/C, and its diffusion-limiting current density is 29% higher than that of commercial Pt/C. The obtained Co-N-GCA is also highly active toward the OER, with a small overpotential of 408 mV at a current density of 10 mA cm⁻². Its overall oxygen electrode activity parameter (ΔE) is 0.821 V, which is comparable to most of the best nonprecious-metal catalysts reported previously. Furthermore, Co-N-GCA demonstrates superior durability in both the ORR and the OER, making it a promising noble-metal-free bifunctional catalyst in practical applications for energy conversion and storage. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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15 pages, 4974 KiB

Open AccessArticle

N,S Co-Doped Carbon Nanofibers Derived from Bacterial Cellulose/Poly(Methylene blue) Hybrids: Efficient Electrocatalyst for Oxygen Reduction Reaction

by Jing Liu, Yi-Gang Ji, Bin Qiao, Fengqi Zhao, Hongxu Gao, Pei Chen, Zhongwei An, Xinbing Chen and Yu Chen

Catalysts 2018, 8(7), 269; https://doi.org/10.3390/catal8070269 - 30 Jun 2018

Cited by 17 | Viewed by 4322

Abstract

Exploring inexpensive and highly efficient electrocatalyst to decrease the overpotential of oxygen reduction reaction (ORR) is one of the key issues for the commercialization of energy conversion and storage devices. Heteroatom-doped carbon materials have attracted increasing attention as promising electrocatalysts. Herein, we prepared a highly active electrocatalyst, nitrogen, sulfur co-doped carbon nanofibers (N/S-CNF), via in situ chemical oxidative polymerization of methylene blue on the bacterial cellulose nanofibers, followed by carbonization process. It was found that the type of nitrogen/sulfur source, methylene blue and poly(methylene blue), has significantly influence on the catalytic activity of the resultant carbon nanofibers. Benefiting from the porous structure and high surface area (729 m²/g) which favors mass transfer and exposing of active N and S atoms, the N/S-CNF displays high catalytic activity for the ORR in alkaline media with a half-wave potential of about 0.80 V, and better stability and stronger methanol tolerance than that of 20 wt % Pt/C, indicating great potential application in the field of alkaline fuel cell. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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13 pages, 4222 KiB

Open AccessFeature PaperArticle

Influence of the Structure-Forming Agent on the Performance of Fe-N-C Catalysts

by Sven Schardt, Natascha Weidler, W. David Z. Wallace, Ioanna Martinaiou, Robert W. Stark and Ulrike I. Kramm

Catalysts 2018, 8(7), 260; https://doi.org/10.3390/catal8070260 - 28 Jun 2018

Cited by 6 | Viewed by 3273

Abstract

In this work, the influence of the structure-forming agent on the composition, morphology and oxygen reduction reaction (ORR) activity of Fe-N-C catalysts was investigated. As structure-forming agents (SFAs), dicyandiamide (DCDA) (nitrogen source) or oxalic acid (oxygen source) or mixtures thereof were used. For characterization, cyclic voltammetry and rotating disc electrode (RDE) experiments were performed in 0.1 M H₂SO₄. In addition to this, N₂ sorption measurements and Raman spectroscopy were performed for the structural, and elemental analysis for chemical characterization. The role of metal, nitrogen and carbon sources within the synthesis of Fe-N-C catalysts has been pointed out before. Here, we show that the optimum in terms of ORR activity is achieved if both N- and O-containing SFAs are used in almost similar fractions. All catalysts display a redox couple, where its position depends on the fractions of SFAs. The SFA has also a strong impact on the morphology: Catalysts that were prepared with a larger fraction of N-containing SFA revealed a higher order in graphitization, indicated by bands in the 2nd order range of the Raman spectra. Nevertheless, the optimum in terms of ORR activity is obtained for the catalyst with highest D/G band ratio. Therefore, the results indicate that the presence of an additional oxygen-containing SFA is beneficial within the preparation. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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13 pages, 5353 KiB

Open AccessFeature PaperArticle

Binary Nitrogen Precursor-Derived Porous Fe-N-S/C Catalyst for Efficient Oxygen Reduction Reaction in a Zn-Air Battery

by Xiao Liu, Chi Chen, Qingqing Cheng, Liangliang Zou, Zhiqing Zou and Hui Yang

Catalysts 2018, 8(4), 158; https://doi.org/10.3390/catal8040158 - 13 Apr 2018

Cited by 9 | Viewed by 4846

Abstract

It is still a challenge to synthesize non-precious-metal catalysts with high activity and stability for the oxygen reduction reaction (ORR) to replace the state-of-the art Pt/C catalyst. Herein, a Fe, N, S co-doped porous carbon (Fe-NS/PC) is developed by using g-C₃N₄ and 2,4,6-tri(2-pyridyl)-1,3,5-triazine (TPTZ) as binary nitrogen precursors. The interaction of binary nitrogen precursors not only leads to the formation of more micropores, but also increases the doping amount of both iron and nitrogen dispersed in the carbon matrix. After a second heat-treatment, the best Fe/NS/C-g-C₃N₄/TPTZ-1000 catalyst exhibits excellent ORR performance with an onset potential of 1.0 V vs. reversible hydrogen electrode (RHE) and a half-wave potential of 0.868 V (RHE) in alkaline medium. The long-term durability is even superior to the commercial Pt/C catalyst. In the meantime, an assembled Zn-air battery with Fe/NS/C-g-C₃N₄/TPTZ-1000 as the cathode shows a maximal power density of 225 mW·cm⁻² and excellent durability, demonstrating the great potential of practical applications in energy conversion devices. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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4892 KiB

Open AccessArticle

Preparation of Ag₄Bi₂O₅/MnO₂ Corn/Cob Like Nano Material as a Superior Catalyst for Oxygen Reduction Reaction in Alkaline Solution

by Xun Zeng, Junqing Pan and Yanzhi Sun

Catalysts 2017, 7(12), 379; https://doi.org/10.3390/catal7120379 - 06 Dec 2017

Cited by 6 | Viewed by 6803

Abstract

Ag₄Bi₂O₅/MnO₂ nano-sized material was synthesized by a co-precipitation method in concentrated KOH solution. The morphology characterization indicates that MnO₂ nanoparticles with a size of 20 nm are precipitated on the surface of nano Ag₄Bi₂O₅, forming a structure like corn on the cob. The obtained material with 60% Mn offers slightly higher initial potential (0.098 V vs. Hg/HgO) and limiting current density (−5.67 mA cm⁻²) at a rotating speed of 1600 rpm compared to commercial Pt/C (−0.047 V and −5.35 mA cm⁻², respectively). Furthermore, the obtained material exhibits superior long-term durability and stronger methanol tolerance than commercial Pt/C. The remarkable features suggest that the Ag₄Bi₂O₅/MnO₂ nano-material is a very promising oxygen reduction reaction catalyst. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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10010 KiB

Open AccessArticle

A Novel Metal–Organic Framework Route to Embed Co Nanoparticles into Multi-Walled Carbon Nanotubes for Effective Oxygen Reduction in Alkaline Media

by Hong Zhu, Ke Li, Minglin Chen, Hehuan Cao and Fanghui Wang

Catalysts 2017, 7(12), 364; https://doi.org/10.3390/catal7120364 - 27 Nov 2017

Cited by 6 | Viewed by 4711

Abstract

Metal–organic framework (MOF) materials can be used as precursors to prepare non-precious metal catalysts (NPMCs) for oxygen reduction reaction (ORR). Herein, we prepared a novel MOF material (denoted as Co-bpdc) and then combined it with multi-walled carbon nanotubes (MWCNTs) to form Co-bpdc/MWCNTs composites. After calcination, the cobalt ions from Co-bpdc were converted into Co nanoparticles, which were distributed in the graphite carbon layers and MWCNTs to form Co-bpdc/MWCNTs. The prepared catalysts were characterized by TEM (Transmission electron microscopy), XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), BET (Brunauer–Emmett–Teller), and Raman spectroscopy. The electrocatalytic activity was measured by using rotating disk electrode (RDE) voltammetry. The catalysts showed higher ORR catalytic activity than the commercial Pt/C catalyst in alkaline solution. Co-bpdc/MWCNTs-100 showed the highest ORR catalytic activity, with an initial reduction potential and half-wave potential reaching 0.99 V and 0.92 V, respectively. The prepared catalysts also showed superior stability and followed the 4-electron pathway ORR process in alkaline solution. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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Review

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43 pages, 11426 KiB

Open AccessReview

Recent Advances of Cobalt-Based Electrocatalysts for Oxygen Electrode Reactions and Hydrogen Evolution Reaction

by Haihong Zhong, Carlos A. Campos-Roldán, Yuan Zhao, Shuwei Zhang, Yongjun Feng and Nicolas Alonso-Vante

Catalysts 2018, 8(11), 559; https://doi.org/10.3390/catal8110559 - 19 Nov 2018

Cited by 108 | Viewed by 16067

Abstract

This review summarizes recent progress in the development of cobalt-based catalytic centers as the most potentially useful alternatives to noble metal-based electrocatalysts (Pt-, Ir-, and Ru-based) towards the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) in acid and alkaline media. A series of cobalt-based high-performance electrocatalysts have been designed and synthesized including cobalt oxides/chalcogenides, Co–N_x/C, Co-layered double hydroxides (LDH), and Co–metal-organic frameworks (MOFs). The strategies of controllable synthesis, the structural properties, ligand effect, defects, oxygen vacancies, and support materials are thoroughly discussed as a function of the electrocatalytic performance of cobalt-based electrocatalysts. Finally, prospects for the design of novel, efficient cobalt-based materials, for large-scale application and opportunities, are encouraged. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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23 pages, 5946 KiB

Open AccessReview

Three-Dimensional Heteroatom-Doped Nanocarbon for Metal-Free Oxygen Reduction Electrocatalysis: A Review

by Dongbin Xiong, Xifei Li, Linlin Fan and Zhimin Bai

Catalysts 2018, 8(8), 301; https://doi.org/10.3390/catal8080301 - 27 Jul 2018

Cited by 33 | Viewed by 5104

Abstract

The oxygen reduction reaction (ORR) at the cathode is a fundamental process and functions a pivotal role in fuel cells and metal–air batteries. However, the electrochemical performance of these technologies has been still challenged by the high cost, scarcity, and insufficient durability of the traditional Pt-based ORR electrocatalysts. Heteroatom-doped nanocarbon electrocatalysts with competitive activity, enhanced durability, and acceptable cost, have recently attracted increasing interest and hold great promise as substitute for precious-metal catalysts (e.g., Pt and Pt-based materials). More importantly, three-dimensional (3D) porous architecture appears to be necessary for achieving high catalytic ORR activity by providing high specific surface areas with more exposed active sites and large pore volumes for efficient mass transport of reactants to the electrocatalysts. In this review, recent progress on the design, fabrication, and performance of 3D heteroatom-doped nanocarbon catalysts is summarized, aiming to elucidate the effects of heteroatom doping and 3D structure on the ORR performance of nanocarbon catalysts, thus promoting the design of highly active nanocarbon-based ORR electrocatalysts. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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19 pages, 3576 KiB

Open AccessReview

Host-Guest Engineering of Layered Double Hydroxides towards Efficient Oxygen Evolution Reaction: Recent Advances and Perspectives

by Jianming Li, Shan Jiang, Mingfei Shao and Min Wei

Catalysts 2018, 8(5), 214; https://doi.org/10.3390/catal8050214 - 17 May 2018

Cited by 26 | Viewed by 8636

Abstract

Electrochemical water splitting has great potential in the storage of intermittent energy from the sun, wind, or other renewable sources for sustainable clean energy applications. However, the anodic oxygen evolution reaction (OER) usually determines the efficiency of practical water electrolysis due to its sluggish four-electron process. Layered double hydroxides (LDHs) have attracted increasing attention as one of the ideal and promising electrocatalysts for water oxidation due to their excellent activity, high stability in basic conditions, as well as their earth-abundant compositions. In this review, we discuss the recent progress on LDH-based OER electrocatalysts in terms of active sites, host-guest engineering, and catalytic performances. Moreover, further developments and challenges in developing promising electrocatalysts based on LDHs are discussed from the viewpoint of molecular design and engineering. Full article

(This article belongs to the Special Issue Novel Non-Precious Metal Electrocatalysts for Oxygen Electrode Reactions)

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