Inorganic Chemistry Frontiers
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2021
·Vol. 8
·期 23
·5034-5044
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IF 6.569
Yu Du,Gentian Yue,Zhang Lan,Yueyue Gao,Jihuai Wu,Furui Tan
Transition metal phosphates have aroused wide attention and been applied in the field of energy conversion due to their high catalytic properties and low cost, but magnetic metal phosphates are rarely used in DSSC. In this work, the magnetic CoP@FeP4 thin film was prepared on carbon paper (CP) using a two-step process and proposed as a counter electrode (CE) for dye-sensitized solar cells (DSSCs). The morphology of CoP@FeP4@CP with a silkworm-like structure is advantageous to enhance the catalytic ability for the interface reaction, establish a good connection between the electrode material and electrolyte, and accelerate the electron transmission. The characterizations using cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel curves all indicate that the CoP@FeP4@CP CE shows excellent electrochemical catalytic performance for the I−/I3− electrolyte. Under optimal conditions, a high power conversion efficiency of 9.88% is achieved for DSSC with CoP@FeP4@CP CE much higher than that of Pt (7.49%) and CoP@CP (8.73%) CEs. This phenomenon can be attributed to the unique chemical structure and the synergistic effect of CoP@FeP4@CP CE. CoP@FeP4@CP CE with the advantages of efficient, low cost, and facile synthesis is a promising alternative to the expensive Pt CE for the DSSCs in the future.
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高影响因子
APPLIED SURFACE SCIENCE
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2020
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IF 6.182
Qiang Zhang,Wei-Bin Zhang,Peng Hei,Zhiqian Hou,Tingshuai Yang,Jianping Long
The self-supported transition metal phosphide with specific morphology and architecture has been investigated extensively due to excellent conductivity, stability, and morphologic diversity. In the work, cobalt phosphide with special nanoprism arrays in-situ grown on the nickel foam skeleton forms a typical three-dimensional open structure. It exhibits notable electrochemical performance when employed as an anode in a single electrode system, which owns a high mass specific capacitance (1349 F g −1 at the current density of 1 A g −1 , which is the highest compared with that in the extant literature), good rate capacity and cycle stability. Besides, pseudocapacitive contribution to the entire capacity is up to about 77%, revealing the nature of high mass specific capacitance of the as-prepared CoP@NF as the working electrode. Furthermore, an asymmetrical supercapacitor device has been fabricated using CoP@NF as an anode and CMK-3@NF as a cathode. It can deliver a high power density of 325 W kg −1 at the energy density of 24 Wh kg −1 and the specific capacitance retention of about 93% after 5000 cycles. The results demonstrate that CoP@NF with special nanoprism arrays is a promising potential candidate as the electrode material of supercapacitors and other energy-storing applications.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2019
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IF 4.084
Zequn Chen,Hongfu Jia,Jingrun Yuan,Xi Liu,Chaohe Fang,Yunying Fan,Chuanbao Cao,Zhuo Chen
To achieve high activity and stability for both hydrogen and oxygen evolution reactions through the non-precious-metal based electrocatalysts is still facing the great challenge. Herein, we demonstrate a facile strategy to prepare CoP nanoparticles (NPs) loaded on N, P dual-doped carbon (NPC) electrocatalysts with high concentration N and P dopants through a pyrolysis-deposition-phosphidation process. The great bifunctional electrocatalytic activity for both HER (the overpotential of 98 mV and 86 mV at 10 mA cm −2 in both 0.5 M H 2 SO 4 and 1 M KOH electrolytes, respectively) and OER (the overpotential of 300 mV at 10 mA cm −2 in 1 M KOH electrolyte) were achieved. When CoP@NPC hybrid was used as two electrodes in the 1 M KOH electrolyte system for overall water splitting, the needed cell potential for achieving the current density of 10 mA cm −2 is 1.6 V, and it also showed superior stability for HER and OER after 10 h’ test with almost negligible decay. Experimental results revealed that the P atoms in CoP were the active sites for HER and the CoP@NPC hybrid showed excellent bifunctional electrocatalytic properties due to the synergistic effects between the high catalytic activity of CoP NPs and NPC, in which the doping of N and P in carbon led to a stronger polarization between Co and P in CoP, promoting the charge transfer from Co to P in CoP, enhancing the catalytic activity of P sites and Co sites in CoP for HER and OER, respectively. Specifically, the improvements could result from the changed charge state, the increased active specific surface area, and the facilitated reaction kinetics by N, P co-doping and admixture. This work provides a high-efficient, low-cost and stable electrocatalyst for overall water splitting, and throws light on rational designing high performance electrocatalysts.
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Journal of Materials Chemistry A
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2019
·Vol. 7
·期 39
·22453-22462
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IF 10.733
Liang Yan,Bing Zhang,Junlu Zhu,Zhonggang Liu,Haiyan Zhang,Yunyong Li
Exploring highly efficient and cost-effective electrocatalysts has become imperative for neutral-pH water splitting, which is environmentally friendly and can reduce the cost of electrolysis systems. Here, we report an effective strategy to design a novel type of callistemon-like Zn and S codoped CoP nanorod clusters by introducing both Zn and S into cobalt phosphide, thereby creating electrocatalysts for highly efficient and stable neutral water splitting. The best Zn and S codoped CoP nanorod clusters on carbon paper (Zn,S–CoP NRCs/CP) require overpotential values of 67 and 391 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at 10 mA cm−2 in 1.0 M phosphate-buffered solution, respectively. Remarkably, this enables a neutral electrolyzer to deliver 10 mA cm−2 at a low cell voltage of 1.70 V, which is superior to those afforded by the Pt/C/CP‖IrO2/CP couple and most of the state-of-the-art electrocatalysts. Impressively, this electrolyzer can be powered by an AA battery (∼1.5 V). Density functional theory computations and systematic experiments have verified that the improved HER and OER activities originate from the optimized electronic structures that can facilitate the adsorption and desorption of hydrogen intermediates after introducing Zn and S and accelerating the formation of oxygenated intermediates on CoOOH, respectively. This work provides a new strategy to boost the performance of transition metal phosphides for neutral water or seawater splitting.
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APPLIED SURFACE SCIENCE
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2019
·
IF 5.155
Huijie Li,Jingli Zhao,Yan Geng,Zhongjun Li,Yike Li,Jianshe Wang
CoP/g-C 3 N 4 , a kind of noble-metal-free binary photocatalyst , has been demonstrated to be active for water splitting. However, high recombination rate of charge carriers is still one of the biggest factors to restrict the photoactivity of CoP/g-C 3 N 4 . In this paper, Boron doped g-C 3 N 4 nanodots (BCNDs) were introduced to CoP/g-C 3 N 4 nanosheets (CoP/CNNS) and a novel CoP/BCNDs/CNNS ternary photocatalyst was constructed. Experimental characterization and testing results indicate that BCNDs/CNNS heterojunction was formed in CoP/BCNDs/CNNS ternary photocatalyst. Comparing with CoP/g-C 3 N 4 , CoP/BCNDs/CNNS facilitates electron-hole separation, and the photocatalytic hydrogen evolution rate can reach 1332.81 μmolg −1 ·h −1 , which is approximately 9.7 times as high as CoP/CNNS. It owns an apparent quantum efficiency of 10.78% at 420 nm. This work would provide a novel strategy to construct high activity g-C 3 N 4 based catalyst without noble metals.
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Advanced Science
·
2022
·Vol. 9
·期 33
·2204192
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IF 17.521
Jiongwei Shan,Wei Wang,Bing Zhang,Xinying Wang,Weiliang Zhou,Liguo Yue,Yunyong Li
Designing dense thick sulfur cathodes to gain high-volumetric/areal-capacity lithium–sulfur batteries (LSBs) in lean electrolytes is extremely desired. Nevertheless, the severe Li 2 S clogging and unclear mechanism seriously hinder its development. Herein, an integrated strategy is developed to manipulate Li 2 S redox kinetics of CoP/MXene catalyst via electron-donor Cu doping. Meanwhile a dense S/Cu 0.1 Co 0.9 P/MXene cathode (density = 1.95 g cm −3 ) is constructed, which presents a large volumetric capacity of 1664 Ah L −1 (routine electrolyte) and a high areal capacity of ≈8.3 mAh cm −2 (lean electrolyte of 5.0 µL mg s −1 ) at 0.1 C. Systematical thermodynamics, kinetics, and theoretical simulation confirm that electron-donor Cu doping induces the charge accumulation of Co atoms to form more chemical bonding with polysulfides, whereas weakens Co S bonding energy and generates abundant lattice vacancies and active sites to facilitate the diffusion and catalysis of polysulfides/Li 2 S on electrocatalyst surface, thereby decreasing the diffusion energy barrier and activation energy of Li 2 S nucleation and dissolution, boosting Li 2 S redox kinetics, and inhibiting shuttling in the dense thick sulfur cathode. This work deeply understands the atomic-level manipulation mechanism of Li 2 S redox kinetics and provides dependable principles for designing high-volumetric-energy-density, lean-electrolyte LSBs through integrating bidirectional electro-catalysts with manipulated Li 2 S redox and dense-sulfur engineering.
研究领域:
材料化学
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电化学
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能源存储
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纳米催化
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固态离子学
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先进电池技术
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CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Libo Zhu,Tiantian Wu,Shuo Bi,Changchun Ke,Chang Chen,Han Tian,Fantao Kong,Xiangzhi Cui,Jianlin Shi
The electrode mass transport limitation during borohydride oxidation reaction (BOR) involving three-phase interfaces greatly deteriorates the performance and energy efficiency of direct sodium borohydride fuel cells (DBFCs). Here we develope a hierarchical structure electrode (HSE) strategy via dispersing Pd clusters on needle-structured CoP-O nanoarrays in situ grown on optimized macro-porous nickel foam (NF), to enhance the solution/gas transport, catalyst utilization and across electrode conductivity, and meanwhile to regulate the OH – -enrichment local environments at the anode of DBFC. The fabricated Pd@CoP-O/NF HSE exhibits excellent BOR catalytic activity featuring a rather low overpotential of 433 mV at 1 A cm −2 and an electron transfer number up to 7.8, and particularly an extra-high power density of 1.23 W cm −2 under O 2 conditions. The watt-level power density of DBFCs is achieved by the adsorption regulations of H*/OH – species on the catalyst and the effective separation and dissipation of bubbles from electrode, which provides an alternative but highly promising pathway for DBFC applications.
研究领域:
能源材料科学
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电化学工程
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燃料电池技术
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高影响因子
RSC Advances
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2018
·Vol. 8
·期 69
·39291-39295
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IF 2.936
Weiming Wu,Xiao-Yuan Wu,Sa-Sa Wang,Can-Zhong Lu
Nanocrystalline transition metal phosphides (CoP and Ni2P) were successfully synthesized by a simple calcination method by using transition metal hydroxides and NaH2PO2 as raw materials. Their catalytic activities for the hydrogen evolution from water electrolysis were evaluated with silicotungstic acid as an electron-coupled-proton buffer, whereby hydrogen and oxygen could be produced separately. It was found that the CoP sample showed higher catalytic activity (32 mmol min−1 g−1) and good stability (12 h) as compared to the Ni2P sample, and its catalytic activity could rival that of the commercial Pt/C catalyst. The electrochemical results revealed that CoP had high cathodic current and small charge transfer resistance, which further suggested it was indeed an efficient noble metal-free catalyst for hydrogen evolution from water electrolysis.
研究领域:
材料科学
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电化学
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催化
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可再生能源
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PubMed
高影响因子
ACS Applied Nano Materials
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2025
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IF 5.5
Hao Ren,Yi Cao,Tianjiao Ling,Junli Zhu,Jifang Xu,Minqi Sheng
Even though cobalt monophosphide (CoP) has been recognized as a prospective alternative to noble metal-based electrocatalysts in alkaline water splitting, further enhancement of the catalytic activity and durability of CoP in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) requires precise manipulation of its nanoscale spatial architecture and surface electronic structure. Herein, tremella-like Pt, B-codoped CoP nanostructures were successfully anchored on carbon cloth (Pt–B–CoP/CC) through a successive process involving wet chemical deposition, surface Pt impregnation, and phosphorization. The resultant Pt–B–CoP/CC exhibits excellent catalytic activity for both HER and OER, primarily attributed to (i) high-density active sites, (ii) enhanced surface conductivity, and (iii) appropriately modulated electronic structure via Pt, B codoping. In addition, Pt–B–CoP/CC exhibits superaerophobicity, enabling the maintenance of efficient exposure of active sites during electrolysis. In an alkaline medium (1.0 M KOH), the required overpotentials are 52.53 (at −10 mA cm–2) for HER and 224.37 mV (at 10 mA cm–2) for OER, which outperform most of the reported transition metal-based bifunctional catalytic electrode materials. The constructed Pt–B–CoP/CC||Pt–B–CoP/CC cell requires an ultralow cell voltage of 1.51 V (1.74 V) to drive a current density of 10 mA cm–2 (100 mA cm–2). After 100 h of continuous electrolysis, the cell voltage increment is almost negligible at 10 mA cm–2, while at 100 mA cm–2 it increases by only 1.97%, demonstrating the tremendous durability of Pt–B–CoP/CC and its potential applicability in industrial-grade electrolyzers. This study provides inspiration for designing and synthesizing advanced multifunctional catalytic electrodes with high efficiency and long-term stability.
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ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2019
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IF 7.149
Huiling Liu,Jinglong Han,Jili Yuan,Chengbin Liu,Dong Wang,Tian Liu,Meijun Liu,Jinming Luo,Aijie Wang,John C. Crittenden
Efficient elimination of antibacterial activity of halogenated antibiotics by dehalogenation pretreatment is desired for a biochemical treatment process. In this study, crystalline cobalt phosphide nanosheet arrays on a Ti plate (C-CoP/Ti) are fabricated by a simple electrodeposition and phosphorization process. The crystalline structure greatly promotes atomic hydrogen (H*) generation. Moreover, the nanosheet arrays can provide abundant active sites and accelerate electron transfer and mass transport. As a result, the dehalogenation rate of florfenicol (FLO, an emerging organic pollutant) on C-CoP/Ti is 11.1, 2.97, and 13.6 times higher than that on amorphous CoP/Ti, Pd/Ti, and bare Ti, respectively. The C-CoP/Ti electrode achieves 97.4% dehalogenation of FLO (20 mg L–1) within 30 min at −1.2 V (vs Ag/AgCl). Nearly 100% of Cl and 20% of F are broken away within 120 min, showing the highest electrocatalytic defluorination efficiency reported so far. Both experimental results and theoretical calculations reveal that the dehalogenation of FLO on C-CoP/Ti is synergistically accomplished via direct reduction of electron transfer and indirect reduction of H*. This study develops a highly efficient non-noble metal electrode material for dehalogenation of halogenated organic compounds.
研究领域:
环境科学
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材料科学
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化学
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PubMed
高影响因子
APPLIED SURFACE SCIENCE
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2026
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IF 6.9
Hui Tang,Xiaobao Chen,Zonghan Huang,Meng Liu,Xiaoping Li,Lanxuan Wen,Yu Liu,Rongwei Li,Songjun Guo,Rongzhi Chen
Inefficiency in photogenerated charge separation, especially within the in-plane heptazine units of widely used carbon nitride semiconductors, severely restricts photocatalytic H 2 evolution. Herein, a dual electric field was constructed in a novel C 3 N 4 /C 3 N 5 /CoP (CNHJ- X /CoP) composite via the synergistic integration of a C 3 N 4 /C 3 N 5 homojunction and a C 3 N 5 /CoP Schottky junction. The optimized CNHJ-5/CoP exhibits a photocurrent density 7.5 times higher than that of pure C 3 N 5 , along with a hydrogen evolution rate of 1878 μmol·g −1 ·h −1 (apparent quantum efficiency = 14.1% at 400 nm), which is 24.5% higher than that of C 3 N 5 /CoP binary composite. X-ray photoelectron spectroscopy, density functional theory calculations, and charge dynamics characterization collectively confirm that the dual electric field enhances the in-plane charge separation efficiency within the C 3 N 5 heptazine units and facilitates the directional transfer of photoelectrons from C 3 N 5 to both C 3 N 4 and CoP. Specifically, the homojunction promotes the retention of more holes in C 3 N 5 for reaction with triethanolamine, while the Schottky junction accelerates electron transfer to CoP for H 2 evolution, thereby driving the forward reaction. This work provides new insights into the design of advanced dual-electric-field systems for enhancing charge separation in two-dimensional nanosheets, thereby boosting photocatalytic H 2 evolution.
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Green Energy & Environment
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2026
·
IF 16.7
Zhen Zhang,Kang Zhou,Xinru Zhao,Armin Rezayan,Dan Wu,Qianli Ma,Zongwu Zhang,Jianshe Wang,Xinqing Chen,Chunbao Xu,Yongsheng Zhang
Water can dissociate on the CoP shell with the formation of H - -Co δ+ -P-O-H + intimate metal-acid sites. • Intimate metal-acid bifunctional sites effectively catalyze the hydrodeoxygenation of furfural to 2-methylfuan. • Brønsted acid sites promote hydrolysis and ring-opening hydrogenolysis of 2-methylfuran to yield 1,4-pentanediol. • Co@CoP catalyst exhibits excellent stability and high activity for the hydrodeoxygenation of various biomass-derived feedstocks. Transition metal phosphides represent promising metal-acid bifunctional catalysts for hydrogenation reactions. However, the origin of the acidity of metal phosphides and their synergistic effects with metallic sites remain poorly understood. Herein, a highly efficient core-shell Co@CoP catalyst prepared via controlled phosphidation of cobalt carbonate was developed for the one-pot transformation of furfural to 1,4-pentanediol. The metallic Co core accelerates active hydrogen transfer, while the CoP shell enables water dissociation to form intimate H - –Co δ+ –P–O–H + metal-acid sites. While the metal-acid bifunctional sites synergistically catalyze the efficient hydrodeoxygenation of furfural to 2-methylfuran intermediate, the Brønsted acid sites on CoP further selectively activate the C–O–C bond of 2-methylfuran, facilitating hydrolysis and ring-opening hydrogenolysis. A 1,4-pentanediol yield of 92.2% is achieved under mild conditions, with excellent cycling stability and applicability for various biomass-derived feedstocks. The disclosed water-engineered Brønsted acidity over metal phosphides provides a fundamental basis for the rational design of bifunctional catalysts for biomass valorization. Co@CoP catalyst enables water dissociation to form intimate H - –Co δ+ –P–O–H + metal-acid sites. While the metal-acid bifunctional sites synergistically catalyze the efficient hydrodeoxygenation of furfural to 2-methylfuran intermediate, the Brønsted acid sites on CoP further selectively activate the 2-methylfuran, facilitating hydrolysis and ring-opening hydrogenolysis. Download: Download high-res image (277KB) Download: Download full-size image
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