ACS Applied Materials & Interfaces
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2016
·
IF 7.145
Weiyong Yuan,Xiaoyan Wang,Xiaoling Zhong,Chang Ming Li
The development of efficient and low-cost hydrogen evolution reaction (HER) catalysts is critical for storing energy in hydrogen via water splitting but still presents great challenges. Herein, we report synthesis of three-dimensional (3-D) hierarchical nanoporous carbon (HNC) supported transition metal phosphides (TMPs) for the first time by in situ growth of CoP nanoparticles (NPs) in CaCO3 NP-templated Cinnamomum platyphyllum leaf extract-derived carbon. They were subsequently employed as a HER catalyst, showing an onset potential of 7 mV and an overpotential of 95.8 mV to achieve 10 mA cm–2, a Tafel plot of 33 mV dec–1, and an exchange current density of 0.1182 mA cm–2, of which the onset overpotential and the Tafel plot are the lowest reported for non-noble-metal HER catalysts, and the overpotential to achieve 10 mA cm–2 and the exchange current density also compare favorably to most reported HER catalysts. In addition, this catalyst exhibits excellent durability with negligible loss in current density after 2000 CV cycles ranging from +0.01 to −0.17 V vs RHE at a scan rate of 100 mV s–1 or 22 h of chronoamperometric measurement at an overpotential of 96 mV and a high Faraday efficiency of close to 100%. This work not only creates a novel high-performance non-noble-metal HER electrocatalyst and demonstrates the great advantages of the in situ grown 3-D HNC supported TMP NPs for the electrocatalysis of HER but also offers scientific insight into the mechanism for the in situ growth of TMP and their precursor NPs, in which an ultralow reactant concentration and rich functional groups on the 3-D HNC support play critical roles.
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高影响因子
Journal of Materials Chemistry A
·
2015
·Vol. 3
·期 43
·21471-21477
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IF 7.443
Miao Xu,Lei Han,Yujie Han,You Yu,Junfeng Zhai,Shaojun Dong
Developing highly efficient and low-cost noble metal-free catalysts toward hydrogen evolution from water splitting is an attractive alternative strategy to solve the ever-increasing environmental contamination and energy demand. Herein, a porous CoP electrocatalyst with a concave polyhedron (CPH) structure was facilely prepared by a topological conversion strategy using Co-MOF (ZIF-67) polyhedrons as the precursor. The morphology of Co-MOFs is well inherited by the as-prepared CoP sample due to the multi-step calcination process at low temperature, which results in the formation of a porous structure. Compared with the contrastive CoP nanoparticles (NPs), the obtained porous CoP CPH electrocatalyst exhibits a remarkably enhanced electrocatalytic performance with a current density of 10 mA cm−2 at an overpotential of 133 mV and a superior durability for the hydrogen evolution reaction (HER) in acid media. A small Tafel slope of ca. 51 mV dec−1 reveals a Volmer–Heyrovsky mechanism during the HER. This work provided a new insight to fabricate morphology-controlled transition metal phosphides with a porous structure via topological conversion, which have importantly potential applications, such as electrocatalysis, photocatalysis and sensors, thanks to their porosity and controllability.
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2021
·Vol. 168
·期 9
·094501
·
IF 4.316
Wei Huang,Jing Tang,Fangyuan Diao,Shuo Li,Hongyu Sun,Xinxin Xiao
Transition metal phosphides are promising oxygen evolution reaction (OER) catalysts due to their earth-abundant and cost-effective features. Here, nanostructured CoP nanoparticles locked in hollow nitrogen doped carbon frameworks (CoP@HNC) were successfully designed and characterized for their morphology, composition, and electrochemistry. In a typical low-temperature phosphorization process, the Co species in carbonized poly-dopamine (PDA) coated ZIF-67 are converted to either hollow CoP or small-sized solid CoP nanoparticles governed by the nanoscale Kirkendall effect. The PDA layers derived nitrogen-doped carbon components feature a hollow polyhedral structure, with CoP nanoparticles imbedded in the shell. CoP@HNC demonstrates a low overpotential of 327 mV for 10 mA cm−2 and a good operational stability (72 h) for alkaline OER. The HNC encapsulation affords the low electronic resistance between CoP nanoparticles, as well as the mechanical and chemical stability of composites by preventing the aggregation of CoP nanoparticles during the OER process.
研究领域:
材料科学
·
电化学
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JOURNAL OF ALLOYS AND COMPOUNDS
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2026
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IF 6.3
Li Sun,Qing Guo,Fan Yang,Kexin Wei,Siyuan Sun,Hongchen Liu,Junpu An,Yang Sun,Yang Guo,Linjie Wang,Yongfeng Li
Rationally designing single-atom catalysts (SACs) with high atomic efficiency and excellent catalytic performance is effective for boosting sodium borohydride (NaBH 4 ) hydrolysis activity. Herein, a series of Pt single-atom catalysts supported on Co-based compounds (Pt/CoP-B, Pt/CoP, Pt/Co 3 O 4 -B) were successfully synthesized via wet impregnation method. Pt M /CoP-B (6.2 wt% Pt loading) exhibited optimal performance at 30 °C: a turnover frequency (TOF) of 1103.26 mol H2 min −1 mol −1 Pt , a hydrogen generation rate (HGR) of 10746 mL min −1 g −1 cat which corresponded to 1.46 times higher than Pt M /Co 3 O 4 -B and 1.33 times higher than Pt M /CoP, outperforming most reported noble metal-based catalysts. It also possessed a low activation energy of 31.05 kJ mol −1 and excellent cycling stability, retaining 95.15 % of initial activity after five consecutive cycles. XPS confirmed strong metal-support interaction between Pt single atoms and CoP-B, which inducing electron transfer from Pt to Co to form electron-deficient Pt and electron-rich Co. DFT calculations revealed that Pt/CoP-B imposes a much lower energy barrier for rate-determining B–H bond cleavage and more effectively promotes H 2 O adsorption. This work offers a new paradigm for creating complementary electronic sites via single-atom-support synergy, opening a novel avenue for advanced NaBH 4 hydrolysis catalysts.
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ELECTROCHIMICA ACTA
·
2021
·
IF 6.901
Huilan Sun,Jian Wang,Wen Li,Fei Yuan,Qiujun Wang,Di Zhang,Bo Wang,Yimin A. Wu
The transition metal phosphide has been widely used as an anode material for lithium and sodium-ion batteries (LIBs and SIBs) due to its high discharge capacity and stable voltage platform. However, some shortcomings such as poor electronic conductivity and low ionic mobility seriously affected its electrochemical performance . To solve these problems, we designed and synthesized the multi-hierarchy structure of Spanish-dagger shaped CoP nanosheets decorated carbon sponge (CoP/CS). The structure is composed of the primary hyperfine CoP nanorods , the secondary micro-size flowers, the tertiary flower/branch carbon skeleton, and the quaternary electrode with a vibrant spatial three-dimensional (3D) network. This unique structure can not only restrict the volume expansion and self-aggregation of CoP but also can reduce the transport length of Li + /Na + . Besides, it has been verified that CoP and CS are bonded by chemical bonds. The CoP/CS electrode has been confirmed to have higher conductivity and lower resistivity than pure CS. Besides, the natural N-doped CS can further provide more active sites for in-situ growth of Co(OH)F precursor (based on the Co-N bonds). As a result, the CoP/CS composite exhibits the impressing capacity (2.4 mAh cm –2 at 0.6 mA cm –2 after 70 cycles in LIBs and 0.834 mAh cm –2 at 0.2 mA cm –2 after 50 cycles in SIBs) and outstanding rate performance. Meanwhile, the excellent cycling stability (0.514 mAh cm –2 at 1 mA cm –2 after 900 cycles) has been verified in SIBs. This work offers a new strategy for the design of multi-hierarchy materials, which may enable the high energy density storage for devices.
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Journal of Energy Chemistry
·
2026
·
IF 15.6
Rong Lin,Yunan Ye,Yuanjie Cao,Hui Liu,Haoran Wang,Shaoda Huang,Qipeng Li,Linjie Zhang,Jinjie Qian
The rational design of heterointerfaces is a potent strategy for optimizing the electronic structure of catalysts, yet achieving site-specific activation at the atomic level remains a formidable challenge. Nevertheless, most reported heterostructures suffer from ill-defined interfaces and non-specific activation, thereby obscuring structure-activity relationships and limiting mechanistic understanding. Herein, we propose a lattice-guided MOF-on-MOF strategy to fabricate an atomically precise CoP/(CoFe)P 2 interface embedded within an N-doped carbon matrix (CoP/(CoFe)P 2 -C). Specifically, the epitaxial growth of CoFe-PBA nanocubes on a MOF-274 template yields a MOF-274@PBA precursor with pre-organized metal domains, which are transformed into intimate phosphide heterojunctions during phosphidation. The optimized CoP/(CoFe)P 2 -C catalyst exhibits exceptional oxygen evolution reaction (OER) activity in alkaline media, requiring an overpotential of only 269 mV to reach 10 mA cm −2 , while demonstrating remarkable structural stability for over 60 h. Furthermore, density functional theory (DFT) calculations reveal that this superior performance stems from a site-specific electronic sacrifice mechanism. At the heterointerface, specific Co sites act as electronic buffers, sacrificially stabilizing unfavorable local configurations. This redistribution optimizes the electronic structure of adjacent Co and Fe sites, collectively lowering the kinetic barrier for *OOH formation and thus enhancing OER kinetics. This work establishes a controllable and generalizable strategy for constructing phosphide heterointerfaces with atomic-level precision, and provides fundamental mechanistic insights into the rational design of advanced OER electrocatalysts through site-specific electronic modulation.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Mengran Lou,Ruiying Wang,Luxiang Wang,Yang Wang,Xinyue Jia,Yuhu Feng,Shengjiao Wen,Yali Cao,Tong Zeng,Zhiqian Li
The development of highly efficient electrocatalysts is critical to advancing overall water splitting (OWS). Herein, a self-supporting composite electrocatalyst based on CoP-Co 2 P/coal-based carbon fibers (CoP-Co 2 P/C-CFs) is successfully fabricated through phase-engineering. The formation mechanism of precursors is investigated, enabling precise modification of CoP and Co 2 P composite phases. This phase-engineering minimizes the Gibbs free energy of hydrogen adsorption, thereby enhancing OWS performance. In addition, the specific active sites involved in the OWS reaction are examined to confirm the effectiveness of phase modulation on CoP and Co 2 P. Furthermore, C-CFs derived from coal exhibit self-supporting properties as well as good acid and alkaline resistances, making them a promising potential candidate for OWS. A two-electrode cell assembled using CoP-Co 2 P/C-CFs exhibits a low voltage of 1.60 V at 10 mA cm −2 for OWS, superior to 1.64 V obtained using Pt/C//RuO 2 . This study not only presents a reliable strategy for obtaining phase-engineered cobalt phosphide catalysts but also outlines a novel approach for coal into high-value-added CFs. Consequently, it offers a new perspective for the development of self-supporting electrocatalysts for OWS.
研究领域:
材料科学
·
能源化学
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CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Zhuoshu Song,Haicheng Xuan,Shasha Liu,Lingxin Meng,Jie Wang,Xiaohong Liang,Yuping Li,Zhida Han,Peide Han
Exploring high active, low cost and stable electrocatalysts to replace noble precious metals has always been the major challenge in overall water splitting applications. Herein, CoFe-layered double hydroxide/Cobalt phosphide heterostructures on nickel foam (CoFe-LDH@CoP/NF) have been synthesized by using hydrothermal, chemical vapor deposition (CVD) and electrodeposition methods. The CoFe-LDH nanosheet is uniformly deposited on the surface of CoP nanowires to create the heterostructure. The formation of heterostructure increases active surface area, accelerates charge transfer velocity, optimizes the kinetics of reaction, thereby significantly improves electrocatalytic activity of the materials. The CoFe-LDH@CoP/NF attains 10 mA cm −2 with a low overpotential of 238 mV for OER and only 63 mV for HER. The catalyst provides the current density of 10 mA cm −2 throughout the overall water splitting by only requiring a low potential of 1.54 V. The CoFe-LDH@CoP/NF as an ideal electrocatalyst provides new ideas for developing efficient non-noble metal-based overall water splitting catalysts.
研究领域:
材料科学
·
电化学
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CARBON
·
2021
·
IF 9.594
Hui Liu,Zihui Liu,Yang Wang,Jinqiang Zhang,Zhongxue Yang,Han Hu,Qingshan Zhao,Hui Ning,Linjie Zhi,Mingbo Wu
The development and optimization of transition metal-based bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are critical for high-efficient water splitting. Herein, we propose a carbon dots-oriented strategy for fabricating nitrogen-doped carbon dots/fungus-like CoP microsphere composite on Ni foam (CoP-NCDs/NF). Owing to its unique structure and the strong interactions between carbon dots and CoP, the newly developed CoP-NCDs/NF electrode exhibits significantly enhanced HER and OER bifunctional catalytic activities, with overpotentials as low as 103 and 226 mV at a current density of 10 mA cm −2 , respectively. Accordingly, the CoP-NCDs/NF displays excellent overall water splitting performance with a low cell voltage of 1.55 V at 10 mA cm −2 and great stability in a two-electrode alkaline electrolyzer. This study provides an alternative pathway on rationally designing and fabricating carbon dots-based materials for high performance water electrolysis and other energy conversion fields.
研究领域:
材料科学
·
能源转换与储存
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2023
·
IF 7.2
Guoliang Gao,Dongwei Wei,Li Li,MingQi Wei,Xueli Chen,Yangyang Yu,Guang Yang,Guang Zhu,Lu Han,Jin Jia
Transition metal phosphates have proved to be promising electrocatalysts for hydrogen evolution reactions (HER) of water splitting, however, further increasing their active sites and catalytic activity remains a major challenge. Herein, accordion-like Co-MOF with layered structure was synthesized. After subsequent carbonization and phosphidization, lamellar heterostructured Co/CoP nanocrystals encapsulated in a P, N co-doped C matrix (Co/CoP@PNC) was obtained. Heterojunction provides abundant active sites and improves electron transfer rate. Additionally, the effect of phosphating degree on the electrocatalytic activity was studied. In the alkaline electrolyte , the current density of the optimized Co/CoP@PNC-10 for HER reached 10 mA cm −2 at overpotential of 137 mV in 1.0 M KOH, which was superior to most of transition metal-based electrocatalysts. This work provides new guidance for the design and development of transition metal-based electrocatalysts.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Yong Xu,Ping Wang,Di Tian,Man Zhang,Weili Dai,Jianping Zou,Shenglian Luo,Xubiao Luo
Photocatalytic CO 2 reduction has been regarded as an ideal method to simulate photosynthesis for achieving carbon neutralization. However, poor charge transfer efficiency limits its development. Herein, an efficient Co/CoP@C catalyst was prepared with compact contact of Co and CoP layer by using MOF as precursor. At the interface of Co/CoP, the difference in functionality between the two phases may result in uneven distribution of electrons, thus forming a self-driven space-chare region. In this region, spontaneous electron transfer is guaranteed, thus facilitating the effective separation of photogenerated carriers as well as boosting the utilization of solar energy. Furthermore, the electron density of active site Co in CoP is increased and more active sites are exposed, which promotes the adsorption and activation of CO 2 molecules. Together with suitable redox potential, low energy barrier for *COOH formation and easy desorption of CO, the reduction rate of CO 2 catalyzed by Co/CoP@C is 4 times higher than that of CoP@C.
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高影响因子
ACS Omega
·
2018
·
IF 0
Yong Xu,Yong Chen,Wen-Fu Fu
CoP was synthesized in situ on the surface of CdS nanowires using a cobalt–ammine complex as a precursor. The generated CoP@CdS photocatalyst was well characterized by X-ray diffraction, transmission electron microscopy, selected-area electron diffraction, and diffuse reflectance spectra. A more efficient charge transfer was successfully achieved owing to the close contact between CoP and CdS. The hybrid photocatalyst showed excellent activity for the reduction of nitroarenes to the corresponding anilines or azobenzene compounds in water. In present work, hydrogen evolution and nitro reduction were concurrent and with the consumption of substrate, the rate of hydrogen evolution increased. The driving force for the reduction originated from the activated hydrogen species in the photocatalytic reaction rather than from dihydrogen. The photocatalytic activity of as-prepared CoP@CdS in situ is comparable to that of the catalysts formed using a noble metal loaded onto CdS. Mechanistic investigation showed that the condensation route is the major pathway for nitro reduction in the present system, and azo compounds could be obtained with less irradiation time, while aniline will be obtained via long-time irradiation.
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