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Metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrids as efficient bifunctional oxygen

《化学科学与工程前沿(英文)》 2022年 第16卷 第9期   页码 1367-1376 doi: 10.1007/s11705-022-2153-3

摘要: The exploration of efficient bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction is pivotal for the development of rechargeable metal–air batteries. Transition metal phosphides are emerging as promising catalyst candidates because of their superb activity and low cost. Herein, a novel metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrid was developed by a carbothermal reduction of cobalt/nickel phosphonate hybrids with different Co/Ni molar ratios. The metal phosphonate derivation method achieved an intimately coupled interaction between metal phosphides and a heteroatom-doped carbon substrate. The resultant Co2P/Ni3P@NC-0.2 enables an impressive electrocatalytic oxygen reduction reaction activity, comparable with those of state-of-the-art Pt/C catalysts in terms of onset potential (0.88 V), 4e selectivity, methanol tolerance, and long-term durability. Moreover, remarkable oxygen evolution reaction activity was also observed in alkaline conditions. The high activity is ascribed to the N-doping, abundant accessible catalytic active sites, and the synergistic effect among the components. This work not only describes a high-efficiency electrocatalyst for both oxygen reduction reaction and oxygen evolution reaction, but also highlights the application of metal phosphonate hybrids in fabricating metal phosphides with tunable structures, which is of great significance in the energy conversion field.

关键词: metal phosphonate     cobalt/nickel phosphide     N-doped carbon     oxygen electrochemistry     Zn−air battery    

Hierarchically porous cellulose nanofibril aerogel decorated with polypyrrole and nickel-cobalt layered

《化学科学与工程前沿(英文)》 2023年 第17卷 第10期   页码 1593-1607 doi: 10.1007/s11705-023-2348-2

摘要: With increasing emphasis on green chemistry, biomass-based materials have attracted increased attention regarding the development of highly efficient functional materials. Herein, a new pore-rich cellulose nanofibril aerogel is utilized as a substrate to integrate highly conductive polypyrrole and active nanoflower-like nickel-cobalt layered double hydroxide through in situ chemical polymerization and electrodeposition. This ternary composite can act as an effective self-supported electrode for the electrocatalytic oxidation of glucose. With the synergistic effect of three heterogeneous components, the electrode achieves outstanding glucose sensing performance, including a high sensitivity (851.4 µA·mmol−1·L·cm−2), a short response time (2.2 s), a wide linear range (two stages: 0.001−8.145 and 8.145−35.500 mmol·L−1), strong immunity to interference, outstanding intraelectrode and interelectrode reproducibility, a favorable toxicity resistance (Cl), and a good long-term stability (maintaining 86.0% of the original value after 30 d). These data are superior to those of some traditional glucose sensors using nonbiomass substrates. When determining the blood glucose level of a human serum, this electrode realizes a high recovery rate of 97.07%–98.89%, validating the potential for high-performance blood glucose sensing.

关键词: cellulose nanofibril     aerogel     nickel-cobalt layered double hydroxide     polypyrrole     nonenzymatic glucose sensor    

Phosphorus-doped Ni–Co sulfides connected by carbon nanotubes for flexible hybrid supercapacitor

《化学科学与工程前沿(英文)》 2023年 第17卷 第5期   页码 491-503 doi: 10.1007/s11705-022-2257-9

摘要: As promising electrode materials for supercapacitors, nickel-cobalt bimetallic sulfides render the advantages of abundant redox reactions and inherently high conductivity. However, in general, unsatisfactory performance of low specific capacity, low rate capability, and fast capacity loss exist in Ni–Co sulfide electrodes. Herein, we rationally regulate phosphorus-doped nickel–cobalt sulfides (P-NCS) to enhance the electrochemical performance by gas–solid phosphorization. Moreover, carbon nanotubes (CNTs) as conductive additives are added to improve the cycle stability and conductivity and form the composite P-NCS/C/CNT. According to density functional theory, more electrons near the Fermi surface of P-NCS are demonstrated notionally than those of simple CoNi2S4. Electrochemical results manifest that P-NCS/C/CNT exhibits superior electrochemical performance, e.g., high specific capacity (932.0 C∙g‒1 at 1 A∙g‒1), remarkable rate capability (capacity retention ratio of 69.1% at 20 A∙g‒1), and lower charge transfer resistance. More importantly, the flexible hybrid asymmetric supercapacitor is assembled using P-NCS/C/CNT and activated carbon, which renders an energy density of 34.875 W·h∙kg‒1 at a power density of 375 W∙kg‒1. These results show that as-prepared P-NCS/C/CNT demonstrates incredible possibility as a battery-type electrode for high-performance supercapacitors.

关键词: cobalt nickel sulfide     phosphorus-doping     hybrid supercapacitor     carbon nanotube     density functional theory    

Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

SUN Guida, LI Cuiqing, ZHOU Zhijun, LI Fengyan

《化学科学与工程前沿(英文)》 2008年 第2卷 第2期   页码 155-164 doi: 10.1007/s11705-008-0038-8

摘要: Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO, -AlO supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/-AlO catalyst. The WP/-AlO catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/-AlO catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/-AlO catalyst. In general, a support or promoter in the WP/-AlO catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.

关键词: tungsten phosphide     differential thermal     catalyst surface     industrial NiW/-AlO     general    

Self-supported transition metal phosphide based electrodes as high-efficient water splitting cathodes

Yan Zhang, Jian Xiao, Qiying Lv, Shuai Wang

《化学科学与工程前沿(英文)》 2018年 第12卷 第3期   页码 494-508 doi: 10.1007/s11705-018-1732-9

摘要:

Electrolytic water splitting has been considered as a promising technology to produce highly pure H2 by using electrical power produced from wind, solar energy or other fitful renewable energy resources. Combining novel self-supporting structure and high-performance transition metal phosphides (TMP) shows substantial promise for practical application in water splitting. In this review, we try to provide a comprehensive analysis of the design and fabrication of various self-supported TMP electrodes for hydrogen evolution reaction, which are divided into three categories: catalysts growing on carbon-based substrates, catalysts growing on metal-based substrates and freestanding catalyst films. The material structures together with catalytic performances of self-supported electrodes are presented and discussed. We also show the specific strategies to further improve the catalytic performance by elemental doping or incorporation of nanocarbons. The simple and one-step methods to fabricate self-supported TMP electrodes are also highlighted. Finally, the challenges and perspectives for self-supported TMP electrodes in water splitting application are briefly discussed.

关键词: transition metal phosphide     self-supported electrode     electrocatalysis     hydrogen evolution reaction    

Synthesis and electrocatalytic property of cubic and spherical nanoparticles of cobalt platinum alloys

Xiaowei TENG, Hong YANG,

《化学科学与工程前沿(英文)》 2010年 第4卷 第1期   页码 45-51 doi: 10.1007/s11705-009-0308-0

摘要: This paper describes the morphological control and electrocatalytic property of CoPt nanoparticles. Both cubic and spherical CoPt nanoparticles were made using cobalt carbonyl and platinum 2,4-pentanedionate under different reaction temperatures in the presence of capping reagents, which included adamantanecarboxylic acid and hexadecylamine. Effects of heterogeneous species on shape of the CoPt nanoparticles were examined by replacing cobalt carbonyl with silver acetylacetonate. Our results suggest that the formation of different shapes of CoPt particles could be attributed to the affinity between cobalt and platinum, and the effects of capping agents. The size and shape dependent electrocatalytic properties of these nanoparticles were examined based on the direct methanol oxidation reaction.

关键词: spherical     2     4-pentanedionate     adamantanecarboxylic     acetylacetonate     electrocatalytic    

Cobalt nanoparticle decorated N-doped carbons derived from a cobalt covalent organic framework for oxygen

《化学科学与工程前沿(英文)》 2021年 第15卷 第6期   页码 1550-1560 doi: 10.1007/s11705-021-2104-4

摘要: The low cost and highly efficient construction of electrocatalysts has attracted significant attention owing to the use of clean and sustainable energy technologies. In this work, cobalt nanoparticle decorated N-doped carbons (Co@NC) are synthesized by the pyrolysis of a cobalt covalent organic framework under an inert atmosphere. The Co@NC demonstrates improved electrocatalytic capabilities compared to N-doped carbon without the addition of Co nanoparticles, indicating the important role of cobalt. The well-dispersed active sites (Co-Nx) and the synergistic effect between the carbon matrix and Co nanoparticles greatly enhance the electrocatalytic activity for the oxygen reduction reaction. In addition, the Co content has a significant effect on the catalytic activity. The resulting Co@NC-0.86 exhibits a superb electrocatalytic activity for the oxygen reduction reaction in an alkaline electrolyte in terms of the onset potential (0.90 V), half-wave potential (0.80 V) and the limiting current density (4.84 mA·cm–2), and a high selectivity, as well as a strong methanol tolerance and superior durability, these results are comparable to those of the Pt/C catalyst. Furthermore, the superior bifunctional activity of Co@NC-0.86 was also confirmed in a home-built Zn-air battery, signifying the possibility for application in electrode materials and in current energy conversion and storage devices.

关键词: cobalt embedment     N-doped carbons     covalent organic framework     oxygen reduction     Zn-air battery    

Enhanced electrochemical performance of CoNiS@TiCT electrode material through doping of cobalt element

《化学科学与工程前沿(英文)》 2023年 第17卷 第10期   页码 1440-1449 doi: 10.1007/s11705-023-2333-9

摘要: The composite electrode of CoNiSx and Ti3C2Tx MXene was successfully prepared using a one-step hydrothermal method under the in-situ doping of the cobalt element. The effects of in-situ doping of the cobalt element on the micromorphology and electrochemical performance of the electrodes were investigated. After in-situ doping of the cobalt element, NiS with a needle-like structure was converted into a CoNiSx with petal-like structure. The petal-like CoNiSx with a rough surface was very dense and evenly wrapped on the surface and interlamination of Ti3C2Tx, which helped increase the specific surface area and pore volume of the electrode. Under the identical test conditions, CoNiSx@Ti3C2Tx had a higher specific capacitance and capacitance retention than NiS@Ti3C2Tx. This result indicated that the in-situ doping of the cobalt element promoted the electrochemical performance of the electrode. The energy density of the CoNiSx@Ti3C2Tx/nickel foam (NF)//activated carbon (AC)/NF asymmetric supercapacitor device was 59.20 Wh·kg–1 at a power density of 826.73 W·kg–1, which was much higher than that of NiS@Ti3C2Tx/NF//AC/NF. Three CoNiSx@Ti3C2Tx/NF//AC/NF in series were able to illuminate the light emitting diode lamp for about 10 min, which was higher than the 5 min of three NiS@Ti3C2Tx/NF//AC/NF in series under the same condition. The CoNiSx@Ti3C2Tx/NF//AC/NF with high energy density had better application potential in energy storage than the NiS@Ti3C2Tx/NF//AC/NF.

关键词: MXene     supercapacitor     cobalt doping     structure characterization     electrochemical performance    

A potentiometric cobalt-based phosphate sensor based on screen-printing technology

Lei ZHU,Xiaohong ZHOU,Hanchang SHI

《环境科学与工程前沿(英文)》 2014年 第8卷 第6期   页码 945-951 doi: 10.1007/s11783-013-0615-z

摘要: A potentiometric cobalt-based screen-printing sensor was fabricated by electroplating cobalt on the surface of a screen-printing electrode as the sensitive layer for the determination of dihydrogenphosphate ( ) in wastewater samples. The electrochemical performance of this sensor was fully examined to determine its detection calibration, detection limit, response time, selectivity, and interference with pH, various ions, and dissolved oxygen (DO). The cobalt-based phosphate sensor showed a phosphate-selective potential response in the range of 10 mol·L to 10 mol·L , yielding a detection limit of 3.16 × 10 mol?L and a slope of -37.51 mV?decade in an acidic solution (pH 4.0) of . DO and pH were found to interfere with sensor responses to phosphate. Ultimately, the performance of the sensor was validated for detecting wastewater samples from the Xiaojiahe Wastewater Treatment Plant against the standard spectrophotometric methods for analysis. The discrepancy between the two methods was generally ±5% (relative standard deviation). Aside from its high selectivity, sensitivity, and stability, which are comparable with conventional bulk Co-wire sensors, the proposed phosphate sensor presents many other advantages, such as low price, compactness, ease of use, and the possibility of integration with other analytical devices, such as flow injectors.

关键词: phosphate     cobalt     screen-printing technology     electroplate     wastewater    

Room temperature oxidation of acetone by ozone over alumina-supported manganese and cobalt mixed oxides

Mehraneh Ghavami, Mostafa Aghbolaghy, Jafar Soltan, Ning Chen

《化学科学与工程前沿(英文)》 2020年 第14卷 第6期   页码 937-947 doi: 10.1007/s11705-019-1900-6

摘要: Volatile organic compounds (VOCs) are among the major sources of air pollution. Catalytic ozonation is an efficient process for removing VOCs at lower reaction temperature compared to catalytic oxidation. In this study, a series of alumina supported single and mixed manganese and cobalt oxides catalysts were used for ozonation of acetone at room temperature. The influence of augmenting the single Mn and Co catalysts were investigated on the performance and structure of the catalyst. The manganese and cobalt single and mixed oxides catalysts of the formula Mn10%-CoX and Co10%-MnX (where X= 0, 2.5%, 5%, or 10%) were prepared. It was found that addition of Mn and Co at lower loading levels (2.5% or 5%) to single metal oxide catalysts enhanced the catalytic activity. The mixed oxides catalysts of (Mn10%-Co2.5%) and (Mn10%-Co5%) led to acetone conversion of about 84%. It is concluded that lower oxidation state of the secondary metal improves ozone decomposition and oxidation of acetone.

关键词: ozone     VOC     manganese oxides     cobalt oxides     alumina support    

Noble-metal-free cobalt hydroxide nanosheets for efficient electrocatalytic oxidation

Jie Lan, Daizong Qi, Jie Song, Peng Liu, Yi Liu, Yun-Xiang Pan

《化学科学与工程前沿(英文)》 2020年 第14卷 第6期   页码 948-955 doi: 10.1007/s11705-020-1920-2

摘要: Cobalt hydroxide has been emerging as a promising catalyst for the electrocatalytic oxidation reactions, including the oxygen evolution reaction (OER) and glucose oxidation reaction (GOR). Herein, we prepared cobalt hydroxide nanoparticles (CoHP) and cobalt hydroxide nanosheets (CoHS) on nickel foam. In the electrocatalytic OER, CoHS shows an overpotential of 306 mV at a current density of 10 mA·cm . This is enhanced as compared with that of CoHP (367 mV at 10 mA·cm ). In addition, CoHS also exhibits an improved performance in the electrocatalytic GOR. The improved electrocatalytic performance of CoHS could be due to the higher ability of the two-dimensional nanosheets on CoHS in electron transfer. These results are useful for fabricating efficient catalysts for electrocatalytic oxidation reactions.

关键词: electrocatalytic oxidation     cobalt hydroxide     nanosheet     water     glucose    

Fischer-Tropsch synthesis by reduced graphene oxide nanosheets supported cobalt catalysts: Role of support

Hasan Oliaei Torshizi, Ali Nakhaei Pour, Ali Mohammadi, Yahya Zamani, Seyed Mehdi Kamali Shahri

《化学科学与工程前沿(英文)》 2021年 第15卷 第2期   页码 299-309 doi: 10.1007/s11705-020-1925-x

摘要: In this paper, a series of cobalt catalysts supported on reduced graphene oxide (rGO) nanosheets with the loading of 5, 15 and 30 wt-% were provided by the impregnation method. The activity of the prepared catalysts is evaluated in the Fischer-Tropsch synthesis (FTS). The prepared catalysts were carefully characterized by nitrogen adsorption-desorption, hydrogen chemisorption, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, temperature programmed reduction, transmission electron microscopy, and field emission scanning electron microscopy techniques to confirm that cobalt particles were greatly dispersed on the rGO nanosheets. The results showed that with increasing the cobalt loading on the rGO support, the carbon defects are increased and as a consequence, the reduction of cobalt is decreased. The FTS activity results showed that the cobalt-time yield and turnover frequency passed from a maximum for catalyst with the Co average particle size of 15 nm due to the synergetic effect of cobalt reducibility and particle size. The products selectivity results indicated that the methane selectivity decreases, whereas the C selectivity raises with the increasing of the cobalt particle size, which can be explained by chain propagation in the primary chain growth reactions.

关键词: cobalt catalyst     cobalt particle size     Fischer-Tropsch synthesis     reduced graphene oxide     supported catalyst    

Activated carbon induced oxygen vacancies-engineered nickel ferrite with enhanced conductivity for supercapacitor

《化学科学与工程前沿(英文)》 2023年 第17卷 第12期   页码 2088-2100 doi: 10.1007/s11705-023-2352-6

摘要: Activated carbon induced oxygen vacancies-engineered nickel ferrite with enhanced conductivity for supercapacitor application

关键词: nickel ferrite conductivity     carbon oxygen vacancies    

Enabling nickel ferrocyanide nanoparticles for high-performance ammonium ion storage

《化学科学与工程前沿(英文)》 2023年 第17卷 第2期   页码 226-235 doi: 10.1007/s11705-022-2198-3

摘要: Prussian blue and its analogs are extensively investigated as a cathode for ammonium-ion batteries. However, they often suffer from poor electronic conductivity. Here, we report a Ni2Fe(CN)6/multiwalled carbon nanotube composite electrode material, which is prepared using a simple coprecipitation approach. The obtained material consists of nanoparticles with sizes 30–50 nm and the multiwalled carbon nanotube embedded in it. The existence of multiwalled carbon nanotube ensures that the Ni2Fe(CN)6/multiwalled carbon nanotube composite shows excellent electrochemical performance, achieving a discharge capacity of 55.1 mAh·g–1 at 1 C and 43.2 mAh·g–1 even at 15 C. An increase in the ammonium-ion diffusion coefficient and ionic/electron conductivity based on kinetic investigations accounts for their high performance. Furthermore, detailed ex situ characterizations demonstrate that Ni2Fe(CN)6/multiwalled carbon nanotube composite offers three advantages: negligible lattice expansion during cycling, stable structure, and the reversible redox couple. Therefore, the Ni2Fe(CN)6/multiwalled carbon nanotube composite presents a long cycling life and high rate capacity. Finally, our study reports a desirable material for ammonium-ion batteries and provides a practical approach for improving the electrochemical performance of Prussian blue and its analogs.

关键词: nickel ferrocyanides     NH4+     electrochemistry     Prussian blue     aqueous ammonium ion batteries    

Molybdenum disulfide@nickel phyllosilicate hybrid for improving the flame retardancy and wear resistance

《化学科学与工程前沿(英文)》 2023年 第17卷 第12期   页码 2114-2126 doi: 10.1007/s11705-023-2357-1

摘要: In this study, nickel phyllosilicate was synthesized based on molybdenum disulfide (MoS2@NiPS) by the sol-gel method, and then MoS2@NiPS was used to prepare epoxy composites. The thermal stability, flame retardancy, and frictional performances of epoxy composites were studied. With the addition of 3 wt% MoS2@NiPS, the epoxy composite increased the limiting oxygen index from 23.8% to 26.1% and reduced the vertical burning time from 166 s for epoxy resin to 35 s. The residual char of the epoxy composite increased from 11.8 to 20.2 wt%. MoS2@NiPS promoted the graphitization of the residual char, and facilitated the formation of a dense and continuous char layer, thereby improving the fire safety of epoxy resin. The epoxy composite with 3 wt% MoS2@NiPS had excellent wear resistance property with a wear rate of 2.19 × 10−5 mm3·N–1·m–1, which was 68.8% lower than that of epoxy resin. This study presented a practical approach to improve the frictional and fire resistance of epoxy composites.

关键词: molybdenum disulfide     nickel phyllosilicate     epoxy resin     flame retardancy    

标题 作者 时间 类型 操作

Metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrids as efficient bifunctional oxygen

期刊论文

Hierarchically porous cellulose nanofibril aerogel decorated with polypyrrole and nickel-cobalt layered

期刊论文

Phosphorus-doped Ni–Co sulfides connected by carbon nanotubes for flexible hybrid supercapacitor

期刊论文

Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

SUN Guida, LI Cuiqing, ZHOU Zhijun, LI Fengyan

期刊论文

Self-supported transition metal phosphide based electrodes as high-efficient water splitting cathodes

Yan Zhang, Jian Xiao, Qiying Lv, Shuai Wang

期刊论文

Synthesis and electrocatalytic property of cubic and spherical nanoparticles of cobalt platinum alloys

Xiaowei TENG, Hong YANG,

期刊论文

Cobalt nanoparticle decorated N-doped carbons derived from a cobalt covalent organic framework for oxygen

期刊论文

Enhanced electrochemical performance of CoNiS@TiCT electrode material through doping of cobalt element

期刊论文

A potentiometric cobalt-based phosphate sensor based on screen-printing technology

Lei ZHU,Xiaohong ZHOU,Hanchang SHI

期刊论文

Room temperature oxidation of acetone by ozone over alumina-supported manganese and cobalt mixed oxides

Mehraneh Ghavami, Mostafa Aghbolaghy, Jafar Soltan, Ning Chen

期刊论文

Noble-metal-free cobalt hydroxide nanosheets for efficient electrocatalytic oxidation

Jie Lan, Daizong Qi, Jie Song, Peng Liu, Yi Liu, Yun-Xiang Pan

期刊论文

Fischer-Tropsch synthesis by reduced graphene oxide nanosheets supported cobalt catalysts: Role of support

Hasan Oliaei Torshizi, Ali Nakhaei Pour, Ali Mohammadi, Yahya Zamani, Seyed Mehdi Kamali Shahri

期刊论文

Activated carbon induced oxygen vacancies-engineered nickel ferrite with enhanced conductivity for supercapacitor

期刊论文

Enabling nickel ferrocyanide nanoparticles for high-performance ammonium ion storage

期刊论文

Molybdenum disulfide@nickel phyllosilicate hybrid for improving the flame retardancy and wear resistance

期刊论文