Nanoscale
·
2024
·Vol. 16
·期 10
·5215-5221
·
IF 5.8
Yangdong Zhou,Junda Chen,Zhiyin Huang,Yuqin Peng,Lixin Xing,Chunmei Tang,Ning Wang,Ling Meng,Mingjie Wu,Lei Du,Siyu Ye
The cathodic oxygen reduction reaction (ORR) has been continuously attracting worldwide interest due to the increasing popularity of proton exchange membrane (PEM) fuel cells. So far, various Pt-group metal (PGM) or PGM-free catalysts have been developed to facilitate the ORR. However, there is still a gap to achieve the expected goals as proposed by the U.S. Department of Energy (DoE). Recently, PGM-free@PGM hybrid catalysts, such as the M/N/C@PtM catalyst, have achieved the milestones of oxygen reduction, as reviewed in our recent work. It is, nevertheless, still challenging to unravel the underlying structure–property relationships. Here, by applying different Pt/Co ratios, a series of Co/N/C@PtxCo catalysts are synthesized. Interestingly, the ORR activity and stability are not linear with the Pt content, but show a volcano-like curve with increased Pt usage. This relationship has been deeply unraveled to be closely related to the contents of pyrrolic N, pyridinic N, and graphitized carbon in catalysts. This work provides guidelines to rationally design the coupled PGM-free@PGM catalysts toward the ORR by appropriate surface engineering.
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Catalysis Science & Technology
·
2025
·
IF 4.2
Canyang Zhang,Yin Liang,Chao Chen,Wei Zhao,Bolong Li,Jianghao Wang,Zhenyu Zhang,Huiping Ji,Feng Zhou,Kaige Wang,Reinout Meijboom,Jie Fu
The decarbonylation of biomass-derived fatty acids (CnH2n+1COOH) presents a sustainable method for producing high-value alkenes (CnH2n). However, the development of efficient and highly selective catalysts for fatty acid decarbonylation remains challenging. In this work, we prepared a series of CoPhPhen/MWCNT-X catalysts by pyrolyzing a 4,7-diphenyl-1,10-phenanthroline (PhPhen) Co complex immobilized on multi-walled carbon nanotubes. In the model decarbonylation reaction of stearic acid, the optimized CoPhPhen/MWCNT-900 catalyst demonstrated remarkable catalytic efficacy, with 81.6% conversion of stearic acid and 58.3% yield of heptadecene. Characterization and comparative experiments demonstrated that the substantial phenyl groups in the PhPhen ligand engage in strong π-π interactions with the MWCNT, effectively inhibiting the migration and aggregation of cobalt single atoms during pyrolysis and thus maintaining a high density of active Co single-atom sites. Further electronic structure investigation revealed that the local electron density around the cobalt species markedly rises with higher pyrolysis temperatures, and this electronic impact exhibits a distinct positive association with the decarbonylation performance of catalysts. In situ DRIFTS was employed to reveal the adsorption and reaction process of fatty acids on the Co single-atom active sites: The fatty acid molecule first coordinates to the cobalt center via the carbonyl oxygen, followed by successive dehydration and decarbonylation processes, finally yielding H2O, CO, and olefins.
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Inorganic Chemistry Frontiers
·
2023
·Vol. 10
·期 8
·2370-2379
·
IF 7
Yanli Ruan,Hang Xu,Haikuo Lei,Wenjuan Xue,Tianyu Wang,Shidong Song,Yangyang Yu,Gui-Rong Zhang,Donghai Mei
Zn–air batteries (ZABs) have been widely studied due to their high theoretical energy density, low cost, and high safety. However, the lack of efficient bifunctional electrocatalysts toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) hinders their large-scale application. Herein, a dendritic NiS2@Co–N–C/CNF nanoarchitecture is proposed, which was fabricated by high-temperature carbonization of Co-MOFs and a subsequent simple hydrothermal composite method using NiS2 nanosheets. The catalyst is reasonably designed to integrate the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) active sites on the surface of carbon nanofibers. Through the synergy between NiS2 and Co–N–C/CNF and the unique branch–leaf porous structure, the catalyst showed excellent catalytic activity and stability. In an alkaline electrolyte, the OER overpotential of NiS2@Co–N–C/CNF is 300 mV at 10 mA cm−2. The ORR half-wave potential (E1/2) of NiS2@Co–N–C/CNF is 0.8 V. In addition, the superior catalytic activity of NiS2@Co–N–C/CNF could be transferred to a ZAB, which exhibits a maximum peak power density of 181 mW cm−2 along with an ultra-long cycling stability for 1050 and 600 h at discharging current densities of 5 and 10 mA cm−2, respectively. The performance is significantly higher than that of commercial precious metal Pt/C + IrO2 mixed catalysts. The peak power density of solid state ZAB (SSZAB) integrated with NiS2@Co–N–C/CNF is 76 mW cm−2, and it can still maintain excellent cycling stability under different bending states. More impressively, four in-series SSZABs (NiS2@Co–N–C/CNFs) can charge smartphones, indicating their potential feasibility in the field of wearable electronics.
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RSC Advances
·
2019
·Vol. 9
·期 58
·33997-34003
·
IF 3.049
Xiao Zhou,Haoran Yu,Yang Liu,Yong Kong,Yongxin Tao,Yong Qin
Co, Al and N tri-doped graphene (CANG) was successfully fabricated via annealing N-doped graphene with Co and Al precursors. The material was characterized by scaning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, physical adsorption, and X-ray photoelectron spectroscopy (XPS). It was found that the as-prepared CANG features a robust three-dimensional hierarchically porous structure. The contents of Co and Al can achieve the maximum value of 2.18 at% and 0.51 at% at the annealing temperature of 950 °C. Upon using the electrocatalyst for the hydrogen evolution reaction (HER), the CANG exhibited remarkable electrocatalytic performance in both acidic (η10 = 105 mV) and alkaline media (η10 = 270 mV), and outperforms Co,N-codoped graphene and Al,N-codoped graphene, respectively. In combination with the density functional theory (DFT) calculations, it was revealed that the introduction of the Al heteroatom can decrease the absolute value of hydrogen adsorption free energy (ΔG(H*)) of Co–N–C catalysts, thus greatly enhancing the HER activity. This discovery will provide new guidance to the design of advanced and inexpensive carbon materials for fuel cell, water-splitting and other electrochemical devices.
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ACTA PHYSICO-CHIMICA SINICA
·
2014
·Vol. 30
·期 1
·150-156
·
IF 0.886
YANG Bing-Jian,WANG Hong,Li Lei,HUANG Bo-Wen,LIAO Xiao-Zhen,HE Yu-Shi,MA Zi-Feng
The development of low-cost and effective electrocatalysts for air electrodes is critical for practical applications of lithium/oxygen batteries. In the present work, phenanthroline (phen) was used as a ligand to prepare a Co(phen)2 complex. The Co(phen)2 complex
was coated on BP2000 and then heat treated at 600, 700, 800, and 900 , to obtain carbon-supported Co-N (Co-N/C) catalysts. The catalytic activities in oxygen reduction reaction/oxygen evolution reaction (ORR/OER) of the prepared catalysts were measured and compared with those of a typical
carbon-supported cobalt tetramethoxyphenylporphyrin (CoTMPP/C) catalyst. The influence of the calcination temperature on the composition and structure of the Co-N/C catalysts was investigated. Electrochemical tests showed that the Co-N/C catalysts prepared at 700 and 800 gave better performances,
comparable to that of the CoTMPP/C catalyst. The superior electrochemical performance of the prepared Co-N/C catalysts and the low cost of the phenanthroline chelating agent make Co-N/C a promising cheap catalyst for lithium/oxygen batteries.
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RARE METALS
·
2026
·Vol. 45
·期 8
·e70443
·
IF 12.1
Weinan Yao,Wenzhuo Sun,Mengjiao Wu,Nana Li,Wenting Li,Xiaotian Guo,Bin He,Huan Pang
en This link goes to a English section zh This link goes to a Chinese section A facile coprecipitation-pyrolysis strategy was employed to fabricate Cu/Co nanoparticles (NPs) embedded in nitrogen-doped carbon matrices (Cu/Co@N-C) through the carbonization of CuCo-MOF precursors. Moreover, monometallic counterparts of Cu@N-C and Co@N-C were also prepared via carbonization of bimetallic CuZn-MOF and CoZn-MOF, respectively. Electrochemical tests confirm that Cu acts as the key active center for nitrite oxidation. By adjusting the Cu/Co molar ratios, a series of cubic Cu/Co@N-C composites with tunable sizes of 200–500 nm were achieved. The synergistic interaction between metallic Cu/Co NPs and the conductive N-C framework enhances catalytic activity and reduces overpotential compared to the monometallic Cu counterpart. The optimized Cu/Co@N-C/glass carbon electrode (GCE) sensor delivered a superior sensitivity as high as 0.461 μA μM −1 cm −2 and wide detection range of 2–10000 μM. The Cu/Co@N-C/GCE sensor also demonstrated superior selectivity, long-term stability of 92.5% retention after 21 days, and reproducibility. This work establishes a versatile approach for engineering various MOF-based catalysts, demonstrating promising potential for applications in environmental monitoring and food safety analysis. 摘要 en This link goes to a English section zh This link goes to a Chinese section 采用一种简便的共沉淀–热解策略 , 以 CuCo-MOF 前驱体为碳源进行碳化 , 成功制备了氮掺杂碳基质负载的 CuCo 双金属纳米颗粒复合材料(Cu/Co@N-C)。此外 , 还分别基于双金属CuZn- MOF和CoZn-MOF碳化制备了Cu@N-C和Co@N-C。电化学测试表明Cu是亚硝酸盐氧化的关键活性中心。通过调控 Cu/Co 摩尔比 , 获得了粒径可调、尺寸范围为 200–500 nm 的立方体 Cu/Co@N-C 复合材料。与单金属Cu@N-C相比 , 金属Cu/Co NPs与导电N-C框架之间的协同作用增强了催化活性并降低了过电位。优化后的 Cu/Co@N-C/玻碳电极(GCE) 传感器表现出优异的电化学传感性能 , 其灵敏度高达 0.461 μA μM −1 cm −2 , 检测范围宽达 2–10000 μM。Cu/Co@N-C/GCE 传感器还展现出优异的选择性、良好的重复性以及长期稳定性 , 在存放21天后仍可保持 92.5% 的电流响应。该工作为构筑各种MOF 基催化材料提供了一种通用策略 , 显示出其在环境监测与食品安全分析领域的广阔应用前景。
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Materials Today Chemistry
·
2026
·
IF 7.4
Yangyang Ren,Zehao Zang,Hua Ning,Guichao Zhang,Lanlan Li,Xiaojing Yang,Zunming Lu,Xinghua Zhang,Xiaofei Yu
Highly graphitic carbon-supported Pt particles (Pt/Co–N–C) was developed. • Regulating the electronic structure of Pt through the strong metal-support interaction. • Intrinsic activity was increased by optimizing O 2 adsorption and lowering energy barrier. • High mass activity and excellent stability of Pt/Co–N–C were achieved. Developing durable supported Pt-based materials is essential for advancing the oxygen reduction reaction in fuel cells, as harsh electrocatalytic conditions often trigger corrosion of carbon supports. The support materials’ physical and chemical properties play a crucial role in the overall performance of Pt-based catalysts. Herein, a highly stable electrocatalyst (Pt/Co–N–C) consisting of small Pt particles coupled tightly with highly graphitized Co–N–C substrate for efficient catalysis was proposed. Pt/Co–N–C exhibited a remarkable mass activity in acidic media, 6.4 times higher than that of commercial Pt/C. Notably, Pt/Co–N–C displayed exceptional stability, with only a 3 mV decrease in half-wave potential and retaining 95.8% mass activity even after 50,000 potential cycles during the accelerated durability tests. Experimental and theoretical analysis highlighted the enhanced support-catalyst and electronic effects between Pt and Co–N–C matrix, thereby enhancing the mass transfer and preventing the structural degradation of the electrocatalyst. This work underscored the possibility of simultaneously modifying Pt active sites and carbon support as effective electrode catalysts in fuel cells. Download: Download high-res image (307KB) Download: Download full-size image
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SYNTHETIC METALS
·
2025
·
IF 4.6
Ran Xu,Man He,Haoyuan Li,Shuangjiang Feng,Yongjuan Wang,Xiaohai Bu,Yuming Zhou
The strategy of customizing MOF-derived electromagnetic wave (EMW) absorbing materials through the construction of precursor size has become a new research direction. While exploring the dimensional adaptability of Co-MOF derivatives in graphene hybrid aerogel for electromagnetic wave absorption is not widely researched, manipulating the compositions and microstructures of EMW absorbing materials has been found to afford superior EMW absorption. Herein, a series of Co-N/C@graphene hybrid aerogel (CNGA) were successfully synthesized by integrating graphene and multi-scale Co-MOF derivatives which are derived from multi-scale Co-MOF precursors. The results displayed the CNGA containing nanoscale Co-MOF derivatives at a 20 wt% filler ratio exhibited the optimal reflection loss (−46.8 dB, 2.7 mm) and the maximum effective absorption bandwidth (5.3 GHz, 2.1 mm). The exceptional EMW absorption properties are credited to the collaborative impact of distinctive loss mechanisms benefited from the small particle size of Co-MOF derivatives in CNGA and appropriate filler ratio. This work demonstrates the correlations between the size of Co-MOF derivatives and electromagnetic parameters of CNGA, and provides a guidance for the development of advanced hybrid aerogel electromagnetic wave absorbing materials.
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JOURNAL OF HAZARDOUS MATERIALS
·
2021
·
IF 10.588
Huiwang Dai,Wenjun Zhou,Wei Wang,Zhiqi Liu
In this study, three Co/N-C catalysts were prepared by pyrolysis of bimetallic zeolitic imidazole frameworks with different Co/Zn ratio, and the critical active Co species in peroxymonosulfate (PMS) activation was investigated. The three catalysts had distinct cobalt species but similar N configuration and graphitization degree. The Co species were distributed as single atoms (Co SAs) at a Co/Zn molar ratio of 1:8, while Co nanoclusters (Co NCs) and Co nanoparticles (NPs) would be formed with further increase in Co content. The degradation efficiency of BPA did not show correlation with the increasing of Co content in catalyst. Based on the catalytic performance comparison and reactive species detection, Co SAs was identified as active sites, which could interact with PMS to generate 1 O 2 via path of PMS→HOO*→O*→ 1 O 2 . However, the role of NCs and NPs in directly activating PMS was negligible. In addition, the increase of Co content in Co/N-C catalyst would result in mass cobalt leaching, which enhanced the BPA degradation via homogeneous catalytic reactions with Co IV as reactive species. It is an effective way to design the Co/N-C catalyst with high catalytic activity and stability via regulating the formation of Co SAs.
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APPLIED SURFACE SCIENCE
·
2017
·
IF 3.387
Yuan Chen,Shanshan Jie,Congqiang Yang,Zhigang Liu
The development of highly active and efficient heterogeneous catalytic oxidation systems has become an attractive research area. In this study, nano cobalt-coordinated nitrogen-doped carbon catalysts (Co-N/C), which were prepared by the pyrolysis of cobalt porphyrin supported on carbon black precursor, were used as highly active catalysts for the oxidation of hydrocarbons with tert -butyl hydroperoxide as the oxidant. The results showed that the catalyst was efficient in the selective oxidation of a variety of saturated (including primary, secondary, and tertiary) C H bonds. The catalyst displayed the best catalytic performance, which was comparable to those for previously reported metal oxide catalysts and even better. The resultant Co-N/C catalysts were characterized in detail by XRD, nitrogen adsorption/desorption isotherms, TEM, SEM and XPS. The homogeneous distribution of the Co species and interactions between the Co-N species could improve the synergistic effect between the Co O, Co N and N C species, which led to their excellent catalytic performance. A first order kinetics was observed for the reaction with the apparent activation energy for ethylbenzene oxidation was 22.2 ± 2.1 kJ mol −1 .
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Science Advances
·
2025
·Vol. 11
·期 9
·
IF 12.5
Mengxue Huang,Xuya Zhu,Wenwen Shi,Qianqian Qin,Jie Yang,Shanshan Liu,Lifang Chen,Ruimin Ding,Lin Gan,Xi Yin
Nitrogen-coordinated metal sites (MNx) in metal- and nitrogen-codoped carbon (M-N-C) catalysts offer promising electrocatalytic activity, but selective synthetic design of MNx sites with specific coordination environments remains challenging. Here, we manipulate the formation statistics of MNx sites by using sacrifice alkali metals (AM = Li, Na, and K) to form metal vacancy-Nx carbon (AM-MVNx-C) templates, which are used to direct the solution-phase formation of CoN4 sites in Co-N-C catalysts. We build a probability weight function based on the embedding energy of M in MNx sites as the descriptor for MNx formation statistics, and we predict that the alkali metals are prone to induce the formation of MVN4 sites. By coordinating Co2+ ions with AM-MVNx-C templates, we synthesize Co-N-C with CoN4 sites, demonstrating remarkable oxygen reduction activity in anion exchange membrane fuel cells. These results highlight the statistical thermodynamics of MNx formation and open up the possibility for the rational design of complex M-N-C electrocatalysts with well-defined MNx sites.
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ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Liming Guo,Xin Wan,Jieyuan Liu,Xu Guo,Xiaofang Liu,Jiaxiang Shang,Ronghai Yu,Jianglan Shui
Synergistic effects have been applied to a variety of hybrid electrocatalysts to improve their activity and selectivity. Understanding the synergistic mechanism is crucial for the rational design of these types of catalysts. Here, we synthesize a MnCo2O4/Co–N–C hybrid electrocatalyst for the oxygen reduction reaction (ORR) and systematically investigate the synergy between MnCo2O4 nanoparticles and Co–N–C support. Theoretical simulations reveal that the synergy is closely related to the distance between active sites. For a pair of remote active sites, the ORR proceeds through the known 2e- + 2e- relay catalysis while the direct 4e– ORR occurs on a pair of adjacent active sites. Therefore, the formation of the undesired byproduct (H2O2) is inhibited at the interface region between MnCo2O4 and Co–N–C. This synergistic effect is further verified on an anion-exchange membrane fuel cell. The findings deepen the understanding of synergistic catalysis and will provide guidance for the rational design of hybrid electrocatalysts.
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