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Journal of Energy Chemistry · 2021 · IF 9.676

Recycling valuable cobalt from spent lithium ion batteries for controllably designing a novel sea-urchin-like cobalt nitride-graphene hybrid catalyst: Towards efficient overall water splitting

Tingting Liu,Sheng Cai,Genfu Zhao,Zhihui Gao,Shuming Liu,Huani Li,Lijuan Chen,Mian Li,Xiaofei Yang,Hong Guo

Along with the continuous consumption in lithium-ion batteries (LIBs), the price of cobalt is inevitably going up in recent years. Therefore, recycling valuable Co element from spent devices, and boosting its service efficiency are becoming two indispensable approaches to promote the utilization of Co in various energy conversion/storage devices. Herein, we realize the recovery of Co from spent LIBs and synthesize a three–dimensional (3D) sea-urchin-like cobalt nitride composite material (labeled as CoN-Gr-2), which is used as a bi-functional catalyst for water splitting. Benefiting from the intrinsic high conductivity, larger surface area and unique 3D sea–urchin–like architecture, CoN-Gr-2 shows an excellent electron transfer efficiency, highly exposed active sites as well as the superior mass transport capacity. The CoN-Gr-2 catalyst exhibits low overpotentials of 128.9 mV and 280 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which are comparable to the commercial 20 wt% Pt/C and RuO 2 catalysts. Moreover, when adopting CoN-Gr-2 as both anode and cathode materials for overall water splitting (in 1.0 M KOH electrolyte), the assembled cell achieves a current density of 10 mA cm −2 at 1.61 V, which almost close to that of Pt/C||RuO 2 benchmark (1.60 V), demonstrating its superior water-splitting efficiency. Meanwhile, the CoN catalysts exhibit strong chemical interaction with the Gr support, suppressing the aggregation of CoN catalysts and maintains their high activity during HER and OER reactions. So, the cell exhibits a high current retention of 97.3% after 40 h. This work successfully develops an industrial chain from recycling Co wastes in spent energy devices to controllably designing 3D sea-urchin-like CoN-Gr with high water splitting efficiency. Therefore, it could further promote the efficient utilization of valuable Co element in various energy devices.

研究领域: 材料科学 · 能源工程 · 催化化学
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DIAMOND AND RELATED MATERIALS · 2020 · IF 2.65

Solubility and stability of diamond in cobalt under 5 GPa

Yi Tian,Junpu Wang,Jiawei Zhang,Shixue Guan,Lu Zhang,Binbin Wu,Yuzhu Su,Mengyang Huang,Li Zhou,Duanwei He

The stability and solubility of diamond in cobalt at a pressure of 5 GPa was investigated. At temperatures ranging from 1000 °C and 1350 °C, diamond can be dissolved in cobalt without graphitization . Meanwhile, the solubility of single diamond crystals in cobalt was measured at 5 GPa and temperatures of up to 1300 °C through weight analysis, and it was found to increase with the increase in temperature. The morphological changes of the diamond crystals after high-pressure and high-temperature (HPHT) treatments were observed using a scanning electron microscope . The resulting quantitative data and morphology analysis enabled the construction of a scheme for the morphological evolution of diamond crystals during their dissolution in cobalt at HPHT. The diamond formation process in cobalt solvent is discussed in relation to the dynamic equilibrium.

CAS / MDL: 7440-48-4
研究领域: 材料科学 · 地质学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Recycling cobalt from spent lithium-ion batteries for designing the novel cobalt nitride followers: Towards efficient overall water splitting and advanced zinc-air batteries

Zhuang Wang,Mian Li,Bin Fu,Wenping Cao,Xiangjie Bo

Although cobalt nitride (CoN)-based nanomaterials have been widely designed as advanced oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR) catalysts, the continuous consumption of lithium-ion batteries (LIBs) has led to a high price of cobalt metal. Therefore, in the future, recycling valuable Co elements from spent devices and boosting their service efficiency will inevitably promote the utilization of Co-based materials in water splitting and zinc-air batteries (ZABs). Herein, we realize the Co recycling from spent LIBs by a simple hydrometallurgy method. Under the assistance of hexamethylenetetramine and polystyrene spheres, after the hydrothermal and pyrolysis treatment in the NH 3 atmosphere, the as-reclaimed cobalt oxalates were successfully transformed into novel three-dimensional (3D) CoN nanoflowers (denoted as CoN NFs). Benefiting from the unique 3D flower-like architectures, intrinsic high conductivity, large surface area, uniformly dispersed CoN nanoparticles, and the synergistic effect between Co 3 N and CoO phases, the 3D flower-like CoN NFs exhibited excellent OER catalytic activity. The performance was much better than commercial RuO 2 in the 1.0 M KOH solution. Furthermore, the CoN NFs-based water splitting cell needed a voltage of 1.608 V to achieve the current density of 10 mA cm −2 , which is even 16 mV smaller than that of Pt/C||RuO 2 benchmark (1.624 V). Meanwhile, the CoN NFs-derived ZAB exhibited a high peak power density of 107.3 mW cm −2 (vs. 103.2 mW cm −2 of Pt/C-RuO 2 -based ZAB) and a low charge–discharge voltage gap (0.93 V vs. 1.43 V of Pt/C-RuO 2 -based ZAB). Due to the excellent structural and elemental stabilities, the corresponding water splitting cell and ZAB had outstanding durability. This work successfully explored an advanced industrial chain from recycling Co metal in spent devices to designing the high-efficiency HER/OER/ORR electrocatalysts for advanced water splitting devices and ZABs. This will further promote the value-added utilization of valuable Co metal in various energy storage or conversion devices.

研究领域: 材料科学 · 能源技术
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Electrochemically assisted preparation of defect-rich Co3O4 electrocatalysts in a water-modified deep eutectic solvent for enhanced oxygen evolution in acid

Xinzhe Shi,Rongrong Deng,Qibo Zhang

Co 3 O 4 -based electrode materials exhibit great potential for utilization as efficient catalysts for the oxygen evolution reaction (OER), especially in acidic media. However, enhancing their catalytic stability remains a crucial challenge. Herein, we present a facile electrochemical deposition approach coupled with calcination treatment to achieve in-situ growth of active Co 3 O 4 films from a deep eutectic solvent with water as the modifier. The incorporation of water optimizes the structure of fabricated Co 3 O 4 by increasing oxygen vacancies and elevating the Co 2+ /Co 3+ ratio, enabling it to sustain the OER in 0.5 M H 2 SO 4 . Impressively, the catalyst grown on Pt/Ti substrate exhibits stable operation over 125 h at 10 mA cm −2 . Attenuated total reflection-fourier transform infrared (ATR-FTIR) spectroscopy reveals that OER on the defect-rich Co 3 O 4 catalyst occurs through both lattice oxygen mediated mechanism (LOM) and adsorption evolution mechanism (AEM).

研究领域: 材料科学 · 电化学
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MINERALS ENGINEERING · 2020 · IF 3.795

A recovery strategy of Sm, Co for waste SmCo magnets by fatty acid based ionic liquids

Qianwen Chen,Shuainan Ni,Guanghua Ai,Tao Zhang,Xiaoqi Sun

Cleaner and lower-cost recovery and separation of samarium(III) and cobalt(II) from waste SmCo magnets can effectively alleviate supply risks of the strategic metals. Based on this goal, a family of renewable, low-cost, biocompatible, non-toxic fatty acid-based ionic liquids (FAILs), including [N1888][DA], [N1888][LA] and [N1888][PA] were synthesized and developed for the separation of Sm(III)/Co(II) from samarium-cobalt simulated solution. The effect factors, i.e. equilibrium time, FAIL molar concentration, salting-out agent concentration and initial pH of aqueous solution were investigated. The extraction mechanism was proposed to be ion association by slope analysis and FT-IR. Under the optimized extraction conditions, a higher purity CoCl 2 (99.5%) product was obtained by a simple extraction-stripping-washing process with the consumption of Na 2 C 2 O 4 and NH 3 ·H 2 O. The produced salty wastewater with lower concentration from the process could be recycled. Sm 2 O 3 with a purity of 99% were obtained by roasting the Sm 2 (C 2 O 4 ) 3 at 800 °C for two hours. The whole process was simple and sustainable, illustrating its potential for industrial applications.

研究领域: 材料科学 · 环境科学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

Good improvement of kinetic properties and catalytic mechanism of MgH2 by spinel-type structure Co3O4

Jinhui Wang,Yuting Li,Quanhui Hou,Peng Jiang,Zhao Ding,Yonglian Xiong

Magnesium-based materials are favored by researchers because of their high hydrogen storage capacity, but they cannot be put to daily use because of their more demanding reaction conditions. Recently, the method to improve the hydrogen storage performance of MgH 2 by catalyst doping has been widely investigated. In this paper, Co 3 O 4 catalysts were prepared by homogeneous precipitation method. It was demonstrated that the Co 3 O 4 catalyst could effectively improve the hydrogen storage performance of MgH 2 . According to the experimental results, the dehydrogenation onset temperature of the MgH 2 +15 wt% Co 3 O 4 composite was about 200 °C, which was about 130 °C lower than that of pure MgH 2 , and the amount of dehydrogenation was 6.26 wt%. The dehydrogenation activation energy of the MgH 2 +15 wt% Co 3 O 4 composite was reduced to 89.13 kJ/mol, which was about 45.7% lower than that of pure MgH 2 . After complete dehydrogenation, the composites started to absorb hydrogen at 50 °C with 6.2 wt%, while the activation energy of reabsorption was also reduced to 47.97 kJ/mol. After 10 cycles of MgH 2 +15 wt% Co 3 O 4 composites, the hydrogen storage capacity of MgH 2 could still be maintained at 99%, which indicated that it had good cycling stability. It was confirmed by various characterizations that Co 3 O 4 was uniformly distributed on the MgH 2 matrix after ball milling . After the first reaction, Co 3 O 4 was converted to CoO, which was uniformly attached to the Mg/MgH 2 surface and stabilized during the cycling process, continuing to provide active sites for hydrogen.

CAS / MDL: 10026-22-9 7439-95-4
研究领域: 材料科学 · 催化化学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2017 · IF 4.421

Au/Co3O4/CeO2 heterostructures: Morphology controlling, junction formation and enhanced catalysis performance

Ping Yang,Yunshi Liu

Co 3 O 4 nanochain and Co 3 O 4 /CeO 2 heterostructures were prepared via an electrospinning process and subsequent calcination . The formation and shape evolution from Co 3 O 4 nanochains to Co 3 O 4 /CeO 2 composite nanobelts were investigated, suggesting that both components and preparation parameters play important roles in resulted morphology and properties. Homogeneous Co 3 O 4 /CeO 2 junctions in belt samples were formed towards enhanced catalysis performance. Well-dispersed Au nanoparticles were deposited on Co 3 O 4 /CeO 2 composite nanostructures or doped inside through reduction and direct calcination route method, respectively. The loading of Au nanoparticles significantly enhanced catalytic performance with onset CO conversion at 100   °C and resulted in CO conversion over at 127   °C.

CAS / MDL: 9003-39-8
研究领域: 材料科学 · 催化化学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2018 · IF 4.229

Cobalt-molybdenum carbide@graphitic carbon nanocomposites: Metallic cobalt promotes the electrochemical hydrogen evolution reaction

Xinran Zhao,Xiaobo He,Fengxiang Yin,Biaohua Chen,Guoru Li,Huaqiang Yin

In this work, a series of metallic cobalt-molybdenum carbide@graphitic carbon (CoMo(x:y)-T@GC) nanocomposites for the electrochemical hydrogen evolution reaction (HER) were synthesized by a sol-gel method. In the as-prepared nanocomposites, β-Mo 2 C and metallic Co coexisted and were encapsulated by graphitic carbon . The presence of metallic Co effectively enhanced the crystallinity of β-Mo 2 C, charge transfer efficiency and electrochemical active surface area (ECSA), thus resulting in the improved HER catalytic activities of the CoMo(x:y)-T@GC nanocomposites. The optimized electrocatalyst CoMo(0.5:0.5)-800@GC required the lowest overpotential of ∼165 mV to deliver a current density of 10 mA cm −2 in 0.1 M KOH, which was at the forefront compared with recently reported Mo 2 C-based electrocatalysts.

CAS / MDL: 12054-85-2 6147-53-1
研究领域: 材料科学 · 电化学
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Journal of Materials Chemistry A · 2017 ·Vol. 5 ·期 11 ·5342-5350 · IF 8.867

A novel gelatin-guided mesoporous bowknot-like Co3O4 anode material for high-performance lithium-ion batteries

Haoran Du,Chao Yuan,Kuangfu Huang,Wenhai Wang,Kai Zhang,Baoyou Geng

A mesoporous bowknot-like Co3O4 material has been synthesized through a facile hydrothermal method, using cobalt nitrate as the cobalt source, urea as the precipitator and gelatin as the guide agent, followed by calcination at 600 °C in air. Morphology characterization reveals that this bowknot-like Co3O4 material possesses a mesoporous structure consisting of nanoparticles. Electrochemical experiments illustrate that the mesoporous bowknot-like Co3O4 anode material exhibits a superior first and 100th reversible specific capacity of 1427.9 mA h g−1 and 1388.8 mA h g−1 at 0.2C, respectively. This material also delivers a high charge capacity of 751.3 mA h g−1 after 150 cycles at 2C. The novel preparation method and satisfactory performance make the bowknot-like Co3O4 a good candidate as a high-performance anode material for use in Lithium-Ion Batteries (LIBs).

研究领域: 材料科学 · 电化学
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Journal of Energy Chemistry · 2019 · IF 5.162

Interface electron collaborative migration of Co–Co3O4/carbon dots: Boosting the hydrolytic dehydrogenation of ammonia borane

Han Wu,Min Wu,Boyang Wang,Xue Yong,Yushan Liu,Baojun Li,Baozhong Liu,Siyu Lu

Ammonia borane (AB) is an excellent candidate for the chemical storage of hydrogen. However, its practical utilization for hydrogen production is hindered by the need for expensive noble-metal-based catalysts. Herein, we report Co–Co 3 O 4 nanoparticles (NPs) facilely deposited on carbon dots (CDs) as a highly efficient, robust, and noble-metal-free catalyst for the hydrolysis of AB. The incorporation of the multi-interfaces between Co, Co 3 O 4 NPs, and CDs endows this hybrid material with excellent catalytic activity ( r B  = 6816 m L H 2 min –1 g Co –1 ) exceeding that of previous non-noble-metal NP systems and even that of some noble-metal NP systems. A further mechanistic study suggests that these interfacial interactions can affect the electronic structures of interfacial atoms and provide abundant adsorption sites for AB and water molecules, resulting in a low energy barrier for the activation of reactive molecules and thus substantial improvement of the catalytic rate.

CAS / MDL: 10026-22-9
研究领域: 材料科学 · 催化化学
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CERAMICS INTERNATIONAL · 2021 · IF 4.527

Holey graphene interpenetrating networks for boosting high-capacitive Co3O4 electrodes via an electrophoretic deposition process

Micun Yun,Yifei Ma,Zhuo Cai,Haomin Ji,Jiemin Han,Mei Wang,Zhaomin Tong,Liantuan Xiao,Suotang Jia,Xuyuan Chen

A composite of Co 3 O 4 /holey graphene (Co 3 O 4 /HG) was prepared via a facile hydrothermal route, and was then processed into an electrode by an electrophoretic deposition process. Holey graphene (HG) wrapped Co 3 O 4 to form a 3D skeleton network, thereby providing high electrical conductivity , and the holes in HG could further shorten the electrolyte ion diffusion pathway. Therefore, by adjusting the mass ratio of Co 3 O 4 to HG, the Co 3 O 4 /HG composite afforded an enhanced capacitance of 2714 F g −1 (at a current density of 1 A g −1 ), which is 20 times higher than that of pure Co 3 O 4 . To further explore the practical applications of Co 3 O 4 /HG, a symmetric supercapacitor employing Co 3 O 4 /HG was fabricated. The supercapacitor functioned stably at potentials up to 1.2 V, with an enhanced energy density of 165 Wh kg −1 and a high power density of 0.6 kW kg −1 at 1 A g −1 .

研究领域: 材料科学 · 能源存储
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APPLIED SURFACE SCIENCE · 2023 · IF 6.7

Exceptionally active and stable RuO2 by constructing p-n heterojunction between Co3O4 and RuO2 for acidic water oxidation

Feng Zhou,Jiadong Chen,Yun Yang,Xiaofeng Ke,Xue Liu,Lijie Zhang,Jun Li,Huile Jin,Shun Wang,Ying Li,Chenliang Su

Development of Ru-based electrocatalysts for acidic oxygen evolution reaction without a trade-off between activity and durability remains challenging. Herein, we constructed Co 3 O 4 /RuO 2 heterojunctions anchored on carbon (Co 3 O 4 /RuO 2 -C) with a low Ru loading (2.74 wt%), in which strong coupled p-n junctions facilitated electron transfer from RuO 2 to Co 3 O 4 . The Co 3 O 4 /RuO 2 -C demonstrated a low overpotential of 170 mV at 10 mA cm −2 and long-term stability in 0.1 M HClO 4 due to its unique structure. The origin of its high performance in acidic OER was revealed by the combination of in-situ attenuated total reflection infrared and Raman tests. Concretely, oxygen generation for Co 3 O 4 /RuO 2 -C was dominated by the adsorbate evolution mechanism, and the introduction of Co 3 O 4 facilitated the redox of RuO 2 , generating active sites for OER. Theoretical calculations further substantiated that the Co 3 O 4 /RuO 2 heterojunctions possessed lower energy barriers for OER. This work provides a compelling synthesis route for effective and stable electrocatalysts for acidic OER.

研究领域: 材料科学 · 电化学 · 催化科学
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