NiCo2S4 nanocrystals anchored on nitrogen-doped carbon nanotubes as a highly efficient bifunctional electrocatalyst for rechargeable zinc-air batteries
TL;DR: In this paper, a new inorganic-nanocarbon coupled hybrid, homogeneous NiCo2S4 nanocrystals anchored on nitrogen-doped carbon nanotubes, has been developed as an extremely efficient bifunctional catalyst to promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for advanced rechargeable zinc-air battery.
About: This article is published in Nano Energy.The article was published on 2017-01-01. It has received 330 citations till now. The article focuses on the topics: Electrocatalyst & Bifunctional catalyst.
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TL;DR: Mixed metal sulfides (MMS) have attracted increased attention as promising electrode materials for electrochemical energy storage and conversion systems including lithium-ion batteries (LIBs), SIBs, hybrid supercapacitors (HSCs), metal-air batteries (MABs), and water splitting as discussed by the authors.
Abstract: Mixed metal sulfides (MMSs) have attracted increased attention as promising electrode materials for electrochemical energy storage and conversion systems including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), hybrid supercapacitors (HSCs), metal–air batteries (MABs), and water splitting. Compared with monometal sulfides, MMSs exhibit greatly enhanced electrochemical performance, which is largely originated from their higher electronic conductivity and richer redox reactions. In this review, recent progresses in the rational design and synthesis of diverse MMS-based micro/nanostructures with controlled morphologies, sizes, and compositions for LIBs, SIBs, HSCs, MABs, and water splitting are summarized. In particular, nanostructuring, synthesis of nanocomposites with carbonaceous materials and fabrication of 3D MMS-based electrodes are demonstrated to be three effective approaches for improving the electrochemical performance of MMS-based electrode materials. Furthermore, some potential challenges as well as prospects are discussed to further advance the development of MMS-based electrode materials for next-generation electrochemical energy storage and conversion systems.
640 citations
631 citations
TL;DR: A perspective for design, preparation, and assembly of air electrodes is proposed for the future innovations of Zn–air batteries with high performance.
Abstract: Zn-air batteries are becoming the promising power sources for portable and wearable electronic devices and hybrid/electric vehicles because of their high specific energy density and the low cost for next-generation green and sustainable energy technologies. An air electrode integrated with an oxygen electrocatalyst is the most important component and inevitably determines the performance and cost of a Zn-air battery. This article presents exciting advances and challenges related to air electrodes and their relatives. After a brief introduction of the Zn-air battery, the architectures and oxygen electrocatalysts of air electrodes and relevant electrolytes are highlighted in primary and rechargeable types with different configurations, respectively. Moreover, the individual components and major issues of flexible Zn-air batteries are also highlighted, along with the strategies to enhance the battery performance. Finally, a perspective for design, preparation, and assembly of air electrodes is proposed for the future innovations of Zn-air batteries with high performance.
602 citations
TL;DR: Light is shed on the controlled synthesis of atomically isolated advanced materials, and deeper understanding is provided on the structure-performance relationships of nanocatalysts with multiple active sites for various catalytic applications.
Abstract: With the inspiration of developing bifunctional electrode materials for reversible oxygen electrocatalysis, one strategy of heteroatom doping is proposed to fabricate dual metal single-atom catalysts. However, the identification and mechanism functions of polynary single-atom structures remain elusive. Atomically dispersed binary Co-Ni sites embedded in N-doped hollow carbon nanocubes (denoted as CoNi-SAs/NC) are synthesized via proposed pyrolysis of dopamine-coated metal-organic frameworks. The atomically isolated bimetallic configuration in CoNi-SAs/NC is identified by combining microscopic and spectroscopic techniques. When employing as oxygen electrocatalysts in alkaline medium, the resultant CoNi-SAs/NC hybrid manifests outstanding catalytic performance for bifunctional oxygen reduction/evolution reactions, boosting the realistic rechargeable zinc-air batteries with high efficiency, low overpotential, and robust reversibility, superior to other counterparts and state-of-the-art precious-metal catalysts. Theoretical computations based on density functional theory demonstrate that the homogenously dispersed single atoms and the synergistic effect of neighboring Co-Ni dual metal center can optimize the adsorption/desorption features and decrease the overall reaction barriers, eventually promoting the reversible oxygen electrocatalysis. This work not only sheds light on the controlled synthesis of atomically isolated advanced materials, but also provides deeper understanding on the structure-performance relationships of nanocatalysts with multiple active sites for various catalytic applications.
484 citations
TL;DR: The spatial isolation of cobalt species on the atomic scale is reported by tuning the zinc dopant content in predesigned bimetallic Zn/Co zeolitic imidazole frameworks (ZnCo-ZIFs), which led to the synthesis of nanoparticles, atomic clusters, and single atoms of Co catalysts on N-doped porous carbon.
Abstract: The size effect of transition-metal nanoparticles on electrocatalytic performance remains ambiguous especially when decreasing the size to the atomic level. Herein, we report the spatial isolation of cobalt species on the atomic scale, which was achieved by tuning the zinc dopant content in predesigned bimetallic Zn/Co zeolitic imidazole frameworks (ZnCo-ZIFs), and led to the synthesis of nanoparticles, atomic clusters, and single atoms of Co catalysts on N-doped porous carbon. This synthetic strategy allowed an investigation of the size effect on electrochemical behavior from nanometer to Angstrom dimensions. Single-atom Co catalysts showed superior bifunctional ORR/OER activity, durability, and reversibility in Zn-air batteries compared with the other derivatives and noble-metal Pt/C+RuO2 , which was attributed to the high reactivity and stability of isolated single Co atoms. Our findings open up a new avenue to regulate the metal particle size and catalytic performance of MOF derivatives.
482 citations
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Book•
01 Jan 1999
TL;DR: Cotton and Wilkinson's Advanced Inorganic Chemistry (AIC) as discussed by the authors is one of the most widely used inorganic chemistry books and has been used for more than a quarter century.
Abstract: For more than a quarter century, Cotton and Wilkinson's Advanced Inorganic Chemistry has been the source that students and professional chemists have turned to for the background needed to understand current research literature in inorganic chemistry and aspects of organometallic chemistry. Like its predecessors, this updated Sixth Edition is organized around the periodic table of elements and provides a systematic treatment of the chemistry of all chemical elements and their compounds. It incorporates important recent developments with an emphasis on advances in the interpretation of structure, bonding, and reactivity.From the reviews of the Fifth Edition:* "The first place to go when seeking general information about the chemistry of a particular element, especially when up-to-date, authoritative information is desired." -Journal of the American Chemical Society.* "Every student with a serious interest in inorganic chemistry should have [this book]." -Journal of Chemical Education.* "A mine of information . . . an invaluable guide." -Nature.* "The standard by which all other inorganic chemistry books are judged."-Nouveau Journal de Chimie.* "A masterly overview of the chemistry of the elements."-The Times of London Higher Education Supplement.* "A bonanza of information on important results and developments which could otherwise easily be overlooked in the general deluge of publications." -Angewandte Chemie.
12,231 citations
TL;DR: The energy that can be stored in Li-air and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed.
Abstract: Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society, for example, extended-range electric vehicles. To go beyond the horizon of Li-ion batteries is a formidable challenge; there are few options. Here we consider two: Li-air (O(2)) and Li-S. The energy that can be stored in Li-air (based on aqueous or non-aqueous electrolytes) and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed. Fundamental scientific advances in understanding the reactions occurring in the cells as well as new materials are key to overcoming these obstacles. The potential benefits of Li-air and Li-S justify the continued research effort that will be needed.
7,895 citations
TL;DR: It is reported that vertically aligned nitrogen-containing carbon nanotubes (VA-NCNTs) can act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction in alkaline fuel cells.
Abstract: The large-scale practical application of fuel cells will be difficult to realize if the expensive platinum-based electrocatalysts for oxygen reduction reactions (ORRs) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, we report that vertically aligned nitrogen-containing carbon nanotubes (VA-NCNTs) can act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction in alkaline fuel cells. In air-saturated 0.1 molar potassium hydroxide, we observed a steady-state output potential of –80 millivolts and a current density of 4.1 milliamps per square centimeter at –0.22 volts, compared with –85 millivolts and 1.1 milliamps per square centimeter at –0.20 volts for a platinum-carbon electrode. The incorporation of electron-accepting nitrogen atoms in the conjugated nanotube carbon plane appears to impart a relatively high positive charge density on adjacent carbon atoms. This effect, coupled with aligning the NCNTs, provides a four-electron pathway for the ORR on VA-NCNTs with a superb performance.
6,370 citations
TL;DR: The Co₃O₄/N-doped graphene hybrid exhibits similar catalytic activity but superior stability to Pt in alkaline solutions, making it a high-performance non-precious metal-based bi-catalyst for both ORR and OER.
Abstract: Catalysts for oxygen reduction and evolution reactions are at the heart of key renewable-energy technologies including fuel cells and water splitting. Despite tremendous efforts, developing oxygen electrode catalysts with high activity at low cost remains a great challenge. Here, we report a hybrid material consisting of Co₃O₄ nanocrystals grown on reduced graphene oxide as a high-performance bi-functional catalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Although Co₃O₄ or graphene oxide alone has little catalytic activity, their hybrid exhibits an unexpected, surprisingly high ORR activity that is further enhanced by nitrogen doping of graphene. The Co₃O₄/N-doped graphene hybrid exhibits similar catalytic activity but superior stability to Pt in alkaline solutions. The same hybrid is also highly active for OER, making it a high-performance non-precious metal-based bi-catalyst for both ORR and OER. The unusual catalytic activity arises from synergetic chemical coupling effects between Co₃O₄ and graphene.
4,898 citations
TL;DR: Taking the step towards successful commercialization requires oxygen reduction electrocatalysts that meet exacting performance targets, and these catalyst systems will need to be highly durable, fault-tolerant and amenable to high-volume production with high yields and exceptional quality.
Abstract: Fuel cells powered by hydrogen from secure and renewable sources are the ideal solution for non-polluting vehicles, and extensive research and development on all aspects of this technology over the past fifteen years has delivered prototype cars with impressive performances. But taking the step towards successful commercialization requires oxygen reduction electrocatalysts--crucial components at the heart of fuel cells--that meet exacting performance targets. In addition, these catalyst systems will need to be highly durable, fault-tolerant and amenable to high-volume production with high yields and exceptional quality. Not all the catalyst approaches currently being pursued will meet those demands.
4,538 citations