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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2021 · IF 4.539

Carbon-based iron-cobalt phosphate FeCoP/C as an effective ORR/OER/HER trifunctional electrocatalyst

Ruge Zhao,Baoxia Ni,Luming Wu,Pingchuan Sun,Tiehong Chen

Efficient catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) are of paramount importance for electrochemical energy applications. Herein, a high-efficient carbon-based trifunctional electrocatalyst FeCoP/C is synthesized through a simple one-step supramolecular-assisted method, in which a supramolecular gel structure is formed by phosphoric acid and melamine to allow the efficient and homogeneous incorporation of highly active species. Experimentally, the as-obtained catalysts exhibit practical trifunctional activities in the ORR, OER, and HER. In alkaline electrolytes , requiring overpotentials of 95 and 282 mV to deliver a current density of 10 mA cm −2 for HER and OER, respectively, and presents the significantly increased alkalic ORR activity, with the half-wave potential of 0.849 V. Furthermore, the FeCoP/C also showed good integrated capabilities for Zn-air batteries. This supramolecular-assisted strategy could bring new inspiration to boost the electrocatalytic performance of transition metal-based electrocatalysts for energy conversion applications.

CAS / MDL: 693-98-1 7664-38-2
研究领域: 材料科学 · 电化学 · 能源转换
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GREEN CHEMISTRY · 2023 ·Vol. 25 ·期 10 ·3966-3973 · IF 9.8

Supercritical CO2-assisted solid-phase etching preparation of MXenes for high-efficiency alkaline hydrogen evolution reaction

Huajian Feng,Qingyong Tian,Junhao Huang,Xinwei Cui,Jingyun Jiang,Yapeng Tian,Li Ye,Qun Xu

Two-dimensional (2D) transition metal carbides, nitrides, or carbonitrides, regarded as MXenes, hold great promise for an extensive range of applications such as efficient catalysis and energy conversion and storage materials. Up to now, various strategies for synthesizing MXenes have been explored, typically including an F-containing aqueous etching process, a molten salt etching method, etc. In this work, for the first time, we have designed a novel solid-phase etching approach to synthesize two-dimensional titanium carbide (MXenes) sheets with the assistance of supercritical CO2 (SC CO2), and the solid-phase etching mechanism behind the efficient fabrication process has also been revealed from a series of characterization methods. It is demonstrated that SC CO2-coated FeF3·3H2O can successfully help realize the delamination of multilayer MXenes into single-layer or few-layer MXenes, and at the same time, the as-prepared MXene sheets are demonstrated to have large surface area and size, high quality and rich fluorine termination groups, which make them efficient in the alkaline hydrogen evolution reaction (HER).

研究领域: 材料科学 · 催化 · 能量转换与存储
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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

A highly efficient and robust hybrid structure of CoNiN@NiFe LDH for overall water splitting by accelerating hydrogen evolution kinetics on NiFe LDH

Jie Wang,Guicai Lv,Cheng Wang

Hydrogen production by electrochemical overall water splitting is considered as a clean and renewable approach for greener energy. However, the efficiency of water electrolysis suffers from the sluggish kinetics and high overpotential of OER. Although NiFe LDH is regarded as a promising OER catalyst, it faces the problem of poor conductivity, resulting in the limitations of HER performance. Herein, a hybrid nano-architecture of CoNiN@NiFe LDH as a bifunctional electrocatalyst for overall water splitting is fabricated via in-situ electrochemically assembling hierarchical NiFe LDH nanosheets on the surface of CoNiN. CoNiN@NiFe LDH shows excellent activities for OER with the overpotentials of 227 and 291 mV to deliver the current densities of 10 and 100 mA cm −2 , respectively. Moreover, an alkaline electrolyzer with CoNiN@NiFe LDH as anode and cathode requires a cell voltage of 1.63 V to achieve 10 mA cm −2 . In addition, the excellent stability with 100 h towards overall water splitting outperforms most transition metal-based bifunctional electrocatalysts. The superior performance is attributed to the abundant active sites, the strong electronic interaction, and the corresponding metal (oxy)hydroxides species generated by in situ surface reconstruction and phase transformation.

研究领域: 材料科学 · 电化学 · 能源转换
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ACS Catalysis · 2021 · IF 13.084

Activating Edge-Mo of 2H-MoS2 via Coordination with Pyridinic N–C for pH-Universal Hydrogen Evolution Electrocatalysis

Jiayi Qin,Cong Xi,Rui Zhang,Tao Liu,Peichao Zou,Deyao Wu,Qianjin Guo,Jing Mao,Huolin Xin,Jing Yang

It is highly desirable to develop all-pH-compatible hydrogen evolution reaction (HER) electrocatalysts that can be used universally in a variety of different electrolyzers and operated in different pH conditions, i.e., acid, alkaline, microbial, chlor-alkali, etc. So far, two-dimensional layered MoS2 and Mo-based carbon materials have been regarded as promising pH-universal HER electrocatalysts. 2H-MoS2 as a naturally occurring and thermodynamically favorable phase, yet still suffers from poor HER activity in neutral and alkaline electrolytes. Herein, a hybrid electrocatalyst, i.e., 2H-MoS2/N-doped mesoporous graphene, rich in interfacial Mo–pyridinic N coordination is fabricated. The optimized hybrid catalyst delivers long-term durability and outstanding HER activity with overpotentials of 110, 145, and 142 mV at 10 mA cm–2 in acidic, alkaline, and phosphate buffered solutions (PBS) media, respectively, outperforming most of the previously reported MoS2-based catalysts. Theoretical and experimental results demonstrate that the interfacial pyridinic N has a higher tendency to bond with Mo atoms than pyrrolic and graphitic N, and the edge-Mo coordinated with pyridinic N could serve as HER active sites. DFT calculations further reveal that Mo–pyridinic N coordination modifies the charge density of edge-Mo, in turn optimizing the hydrogen absorption energy and facilitating water dissociation, and thereby significantly promoting the intrinsic catalytic activity for the pH-universal HER process.

研究领域: 材料科学 · 电化学 · 催化科学
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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2022 · IF 10.319

Interfacial engineering regulated by CeOx to boost efficiently alkaline overall water splitting and acidic hydrogen evolution reaction

Jian Chen,Zhen Hu,Yang Ou,Qinghua Zhang,Xiaopeng Qi,Lin Gu,Tongxiang Liang

Development of a low-cost and durable bifunctional electrocatalyst with high catalytic activity by hybridizing rare earth metal and non-noble metal is of utmost significance. Herein, a bifunctional electrocatalyst consisting of MoO 2 and CeO x heterostructure is synthesized via interfacial engineering. Particularly, due to its unique hetero-interface with abundant oxygen vacancies, the MoO 2 -CeO x /NF is able to exhibit outstanding hydrogen evolution reaction (HER) performance with an overpotential of 26 mV at 10 mA cm −2 , and a preferable oxygen evolution reaction (OER) overpotential of 272 mV at 100 mA cm −2 in 1 M KOH. The recorded HER and OER overpotentials of MoO 2 -CeO x /NF are clearly smaller than those of Pt/C (HER overpotential of 27 mV) and RuO 2 (OER overpotential of 393 mV) at the same current density. More importantly, MoO 2 -CeO x /NF can also exhibit good HER activity with an overpotential of 50 mV at 10 mA cm −2 in acidic media. Thus, it is expected that this work can offer a new approach in the realization of high-catalytic alkaline overall water splitting and acidic HER performance through the rational design of rare-earth metal and non-noble metal heterostructure.

研究领域: 材料科学 · 电化学 · 催化 · 能源材料
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2020 · IF 16.683

Nitrogen-doped carbon wrapped Co-Mo2C dual Mott–Schottky nanosheets with large porosity for efficient water electrolysis

Pengfei Zhang,Yaoda Liu,Tingting Liang,Edison Huixiang Ang,Xu Zhang,Fei Ma,Zhengfei Dai

Efficient, inexpensive and stable electrocatalysts are challenging and desperately required in order to complement the water electrolysis of noble metal catalysts. Herein, a porous nitrogen-doped carbon wrapped Co-Mo 2 C dual Mott–Schottky heterostructure has been successfully fabricated by carbonization of Co-Zn bimetal metal-organic framework (MOF) for water electrolysis. The heterostructure is found to feature with Co and Mo 2 C nanoparticles uniformly encapsulated in the highly porous leaf-like N-doped carbon nanosheet matrix. Such a thin porous dual-Mott–Schottky configuration can afford abundant surface active sites and the boosted electron transfer to promote the water splitting. As for hydrogen/oxygen evolution reaction (HER/OER), it has demonstrated fast kinetics and low overpotentials of 92 mV (HER) and 338 mV (OER) at a current density of 10 mA cm −2 in 1 M KOH. Furthermore, the overall water splitting is stably delivered with a low cell voltage of 1.68 V at 10 mA cm -2 in 1 M KOH. Density function theory (DFT) calculations demonstrate that the interface correlation is favorable to water transfer by electron and speeds up adsorption and water dissociation. The work here opens up interesting possibilities for the rational design and innovation of MOF derived Mott–Schottky electrocatalysts for highly efficient water electrolysis.

研究领域: 材料科学 · 电化学 · 催化
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2024 · IF 8.1

Urea-induced low crystallization of Rh nanoparticles for efficient H2 production

Guangxia Wang,Wenhui Wang,Xiuwei Sun,Liwen Zhou,Yongming Sui,Fuxin Wang,Dezhou Zheng,Zheng Liu,Qi Feng

Developing highly efficient catalysts for the hydrogen evolution reaction (HER) is crucial for advancing renewable hydrogen energy technologies. Heterophase nanomaterials have shown great promise in catalysis, owing to the synergistic effect among various phases and the abundance of active sites located at the phase boundaries or interfaces. However, achieving precise control over these phase structures during synthesis remains a significant challenge. In this work, we explored a one-pot synthesis method for amorphous/crystalline heterophase Rh nanoparticles, with crystallinity tunable by adjusting the quantity of urea and reaction duration. Due to the increased electrochemical active sites, enhanced electron transport, the resulting amorphous/crystalline heterophase Rh exhibits superior HER activities in both acidic (with an overpotential of 27 mV) and alkaline media (with an overpotential of 21 mV), surpassing that of commercial Pt/C and crystalline Rh. Theoretical calculations indicate that the amorphous/crystalline structure reduces the kinetic barrier for water splitting and optimizes adsorption free energy of hydrogen (ΔG H∗ ), thereby enabling the catalyst to exhibit significantly enhanced HER performance. This exploration offers a valuable reference for designing amorphous/crystalline heterophase structures and demonstrates the great potential of phase engineering strategy in the development of electrocatalysts.

CAS / MDL: 57-13-6
研究领域: 材料科学 · 催化化学
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Journal of Materials Chemistry A · 2018 ·Vol. 6 ·期 41 ·20100-20109 · IF 9.931

A “MOFs plus MOFs” strategy toward Co–Mo2N tubes for efficient electrocatalytic overall water splitting

Xia Shi,Aiping Wu,Haijing Yan,Lin Zhang,Chungui Tian,Lei Wang,Honggang Fu

The rational combination of early-transition metal nitrides (ETMNs) with late-transition metals (LTMs) is a promising method for the design of highly efficient catalysts. Herein, we report the design of Co–Mo2N tubes based on a “MOFs plus MOFs” strategy for efficient electrocatalytic water splitting in 1 M KOH. The 1-D Mo-MOFs (Mo source) were prepared in large quantities by the reaction of imidazole with MoO3. ZIF-67 (Zeolitic Imidazolate Framework-67) (Co source) was then grown on the 1-D Mo-MOFs (Mo-based metal–organic frameworks) to obtain ZIF-67/Mo-MOFs by a solution-phase assembly method. The effective combination is due to the similarity of the ligands in the two MOFs. After nitriding, the ZIF-67 was converted into Co metal, and Mo-MOFs were converted into hollow Mo2N, thus giving a hollow Co–Mo2N hybrid with a Co outer layer on the Mo2N inner core. The ratio of Co and Mo in Co–Mo2N can be easily tuned to give optimized catalysts. The tests indicated that the combination of Co and Mo2N can significantly boost the HER performance of materials. At the current density of 10 mA cm−2, the overpotential (η10) on Co–Mo2N was only 76 mV, which is much lower than 296 mV for Mo2N derived from Mo-MOFs and 180 mV for Co–carbon from ZIF-67. The hybrid has also shown improved OER activity in comparison with Mo2N and Co; therefore, the Co–Mo2N can be used as both anode and cathode for an overall water-splitting cell with η10 of 1.576 V. The improved HER activity can be ascribed to the intimate contact between Co and Mo2N for optimized adsorption on reagents, the tube-like structure for easy mass transfer and the good conductivity of Mo2N, which is favourable for transmitting charge.

研究领域: 材料科学 · 化学工程 · 能源科学
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JOURNAL OF POWER SOURCES · 2017 · IF 6.395

Direct selenylation of mixed Ni/Fe metal-organic frameworks to NiFe-Se/C nanorods for overall water splitting

Bo Xu,He Yang,Lincheng Yuan,Yiqiang Sun,Zhiming Chen,Cuncheng Li

Development of low-cost, highly active bifunctional catalyst for efficient overall water splitting based on earth-abundant metals is still a great challenging task. In this work, we report a NiFe-Se/C composite nanorod as efficient non-precious-metal electrochemical catalyst derived from direct selenylation of a mixed Ni/Fe metal-organic framework. The as-obtained catalyst requires low overpotential to drive 10 mA cm −2 for HER (160 mV) and OER (240 mV) in 1.0 M KOH, respectively, and its catalytic activity is maintained for at least 20 h. Moreover, water electrolysis using this catalyst achieves high water splitting current density of 10 mA cm −2 at cell voltage of 1.68 V.

研究领域: 材料科学 · 电化学
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Nanoscale · 2021 ·Vol. 13 ·期 42 ·17953-17960 · IF 7.79

Constructing urchin-like Ni3S2@Ni3B on Ni plate as a highly efficient bifunctional electrocatalyst for water splitting reaction

Yuanyuan Wu,Junqiang Yin,Wei Jiang,Hongji Li,Chunbo Liu,Guangbo Che

Developing efficient and promising non-noble catalysts that can promote both the HER and OER in the same electrolyte is vital. Currently, these reported bifunctional catalysts show only moderate electrocatalytic water-splitting performance, which is much lower than expected. In addition, most of these promising nonprecious electrocatalysts work well only at small current densities (e.g. 10 mA cm−1), but at large current densities their stability and activity are far from satisfactory for practical applications. Herein, we have successfully constructed an urchin-like Ni3S2@Ni3B heterostructure electrocatalyst on Ni plates. The resulting material exhibits great catalytic activities for both the HER and OER, even at large current densities, reaching a current density of 1000 mA cm−l at relatively low applied overpotentials of 517 and 632 mV, respectively. The excellent catalytic performance of Ni3S2@Ni3B/NP is found to benefit from the effective integration of the unique surface structure and the interface electronic structure.

研究领域: 电化学 · 材料科学 · 催化
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INTERNATIONAL JOURNAL OF ENERGY RESEARCH · 2020 ·Vol. 44 ·期 6 ·4827-4836 · IF 3.741

Electrocatalytic hydrogen evolution properties of anionic NiS2-Ni(OH)2 nanosheets produced on the surface of nickel foam

Mojie Sun,Zhao Wang,Bixue Gao,Shijie Wang,Chi Wang,Xiaochen Song,Dongyao Lin

Summary To circumvent the expensive cost of precious metal electrocatalysts, a hydrothermal method and a plasma-enhanced chemical vapor deposition (PECVD) method have been used to prepareNiS 2 -Ni(OH) 2 /NF-PECVD (N-PECVD) with excellent properties. After XRD, SEM, XPS, and other characterization methods, it can be seen that after the hydrothermal reaction of Ni foam (NF), 50-60 nm Ni(OH) 2 nanosheets have grown on the NF frame. The subsequent PECVD reaction produces 90 nm NiS 2 -Ni(OH) 2 nanosheets on the NF frame. The hydrogen release overpotentials in the acidic solution and alkaline solution are 90 and 95 mV ( j = 10 mA/cm 2 ), respectively. And the Tafel slopes reach 80 and 83.6 mV/dec, respectively. The chronopotential (CP) test shows that the material has good HER stability over 12 h. The results from the subsequent electric double layer capacitance and alternating current impedance (EIS) tests show that N-PECVD synthesized by PECVD has a relatively large active electrochemical surface area (ECSA) and a low electrochemical impedance. This study not only finds good inspiration for the synthesis of cheap HER catalysts but also provides a valuable reference for the synthesis of materials in other fields.

CAS / MDL: 1310-58-3 62-56-6
研究领域: 材料科学 · 电化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Nickel-decorated RuO2 nanocrystals with rich oxygen vacancies for high‐efficiency overall water splitting

Xinyu Chen,Jiexi Song,Yifei Xing,Yanqing Qin,Jianbin Lin,Xiao Qu,Bianjing Sun,Shiyu Du,Diwei Shi,Chuntao Chen,Dongping Sun

Designing transition metal-oxide-based bifunctional electrocatalysts with excellent activity and stability for OER/HER to achieve efficient water splitting is of great importance for renewable energy technologies. Herein, a highly efficient bifunctional catalysts with oxygen-rich vacancies of nickel-decorated RuO 2 (NiRuO 2−x ) prepared by a unique one-pot glucose-blowing approach were investigated. Remarkably, the NiRuO 2−x catalysts exhibited excellent HER and OER activity at 10 mA cm −2 in alkaline solution with only a minimum overpotential of 51 mV and 245 mV, respectively. Furthermore, the NiRuO 2−x overall water splitting exhibited an ultra-low voltage of 1.6 V to obtain 10 mA cm −2 and stability for more than 10 h. XPS measurement and theoretical calculations demonstrated that the introduction of Ni-dopant and oxygen vacancies make the d-band center to lie close to the Fermi energy level, the chemical bonds between the active site and the adsorbed oxygen intermediate state are enhanced, thereby lowering the reaction activation barriers of HER and OER. The assembly of solar-driven alkaline electrolyzers facilitate the application of the NiRuO 2−x bifunctional catalysts.

研究领域: 材料科学 · 可再生能源技术
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