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P-Ni4Mo Catalyst for Seawater Electrolysis with High Current Density and Durability
July 2022Vol. 41, Issue 7 Previous issue Next issue
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Guest EditorialStructural Chemistry in Energy Relevant-Catalysis ReactionXinlong Tian*, Jiayuan Li*, Lixue Zhang* and Yu Chen*
Chin. J. Struct. Chem. 2022, 41, 2207001 DOI: 10.14102/j.cnki.0254-5861.2022-0160
July 18, 2022
electrocatalysis
ABSTRACT
Challenges are faced for rapid economic and social development including the global energy shortage, diversification in energy and chemical raw materials, and ecological environmental protection. The development of renewable energy has become a common concern for the current society. Energy relevant-catalysis reaction is the core of energy conversion and chemical processes, aiming to achieve high energy power sources, conversion of reaction feedstocks, and selectivity of target products under mild conditions. More than 85% of energy and chemical processes are closely related to catalysis reaction, that is, driven by highly effective catalysts. It is significant to establish the structural performance relationship by deciphering the atomic structure and electronic states of active sites, which provides new sights into the catalytic processes and promotes the development of novel catalyst materials. Therefore, as supported by Chinese Journal of Structural Chemistry, a special issue for the Structural Chemistry in Energy Relevant-Catalysis Reaction was organized by the Guest Editors. -
PerspectiveTo Break the Limit of Catalytic Site Density of Fe-NCsDongxue Yu and Jiong Wang*
Chin. J. Struct. Chem. 2022, 41, 2207002-2207003 DOI: 10.14102/j.cnki.0254-5861.2022-0165
July 18, 2022
Fe-NC catalysts, site density, oxygen reduction reaction
ABSTRACT
Rational design of Fe and N co-doped carbon catalysts (Fe-NCs), one promising non-precious cathode catalyst, is critical to commercialization of proton exchange membrane fuel cells. The atomic Fe site density of Fe-NCs is critical to improve catalytic currents approaching industrial levels. One recent research proposes a template-guided strategy to break the limit of Fe site density, and greatly promotes the fuel cell performance. -
ReviewDevelopment of Transition Metal Nitrides as Oxygen and Hydrogen ElectrocatalystsXuesheng Yan, Daijie Deng, Suqin Wu, Henan Li and Li Xu*
Chin. J. Struct. Chem. 2022, 41, 2207004-2207015 DOI: 10.14102/j.cnki.0254-5861.2022-0036
July 18, 2022
transition metal nitrides, hydrogen, oxygen, improvement strategies, electrocatalysts
ABSTRACT
With the increasing demand for energy, various emerging energy storage/conversion technologies have gradually penetrated human life, providing numerous conveniences. The practical application efficiency is often affected by the slow kinetics of hydrogen or oxygen electrocatalytic reactions (hydrogen evolution and oxidation reactions, oxygen evolution and reduction reactions) among the emerging devices. Therefore, the researchers devote to finding cost-effective electrocatalysts. Non-noble metal catalysts have low cost and good catalytic activity, but poor stability, agglomeration, dissolution, and other problems will occur after a long cycle, such as transition metal oxides and carbides. Transition metal nitrides (TMNs) stand out among all kinds of non-noble metal catalysts because of the intrinsic platinum-like electrocatalytic activities, relatively high conductivity, and wide range of tunability. In this review, the applications of TMNs in electrocatalytic fields are summarized based on the number of metals contained in TMNs. The practical application potentials of TMNs in fuel cell, water splitting, zinc-air battery and other electrochemical energy storage/conversion devices are also listed. Finally, the design strategies and viewpoints of TMNs-based electrocatalyst are summarized. The potential challenges of TMNs-based electrocatalyst in the development of electrocatalytic energy devices in the future are prospected. -
ReviewAdvances of PtRu-Based Electrocatalysts for Methanol OxidationWei Qiao, Xingyu Huang and Ligang Feng*
Chin. J. Struct. Chem. 2022, 41, 2207016-2207034 DOI: 10.14102/j.cnki.0254-5861.2022-0098
July 18, 2022
Pt-Ru based catalysts, electrocatalysis, methanol oxidation reaction, regulation strategies
ABSTRACT
Platinum-Ruthenium (PtRu)-based materials are considered the “holy grail” of electrocatalysts for methanol oxidation reaction (MOR) in the fuel cells technique. However, to the best of our knowledge, the exhaustive review report on the advance of PtRu materials for methanol oxidation is rarely summarized for the recent novel achievements. Herein, we summarize and discuss the latest progress of PtRu-based catalysts in MOR. The reaction mechanism of MOR is firstly introduced, and the promotion mechanism is revealed by the relevant activity descriptor, the in-situ spectroscopic analysis and the theoretical calculation. Subsequently, some advanced regulation strategies of PtRu-based catalysts are concluded, including support engineering, morphology design and surface interface regulation. Finally, the challenges and opportunities to improve the MOR performance of PtRu-based electrocatalysts are prospected to further promote the widespread application of PtRu-based catalysts in electrocatalytic systems. It is concluded that many efforts are still required to decipher the atomic scale structure-activity relationship and the structural changes of atoms and electrons in the reaction process by advanced strategies and characterization methods. Hopefully, this review can be helpful for novel PtRu-based catalyst development and understanding their correlation to the structure and performance of energy-relevant electrocatalysis. -
CommunicationPhytate-Coordination Triggered Enrichment of Surface NiOOH Species on Nickel Foam for Efficient Urea ElectrooxidationJiayuan Li*, Yuefei Li, Qingyu Xue, Yuchi Gao and Yuanyuan Ma
Chin. J. Struct. Chem. 2022, 41, 2207035-2207039 DOI: 10.14102/j.cnki.0254-5861.2022-0095
July 18, 2022
phytates, surface coordination, urea electrooxidation reaction, electrocatalysis
ABSTRACT
Nickel (Ni)-based materials are promising electrocatalysts for the urea electrooxidation reaction, as the in situ formed NiOOH species on their surface during operation are catalytically active sites. In this work, phytate-coordinated Ni foam (PA-NF) is shown to deliver a high catalytic performance toward the urea electrooxidation reaction, with a low potential of 1.38 V at 10 mA/cm2, a low Tafel slope of 64.1 mV/dec, and superior catalytic stability; a performance comparable to state-of-the-art Ni-based catalysts. Electrochemical characterization alongside the control experiments revealed that such a high performance could be ascribed to kinetically-accelerated surface reconstruction and the enrichment of NiOOH active species on the PA-NF surface during the electrooxidation of urea owing to PA-coordination induced upshift of d-band center of Ni sites. Overall, a new strategy is provided for the design of an efficient and universal Ni-based catalyst for the electrooxidation of urea, which can also be extended to other transition-metal-based systems. -
CommunicationRational Design of Electrocatalyst with Abundant Co/MoN Heterogeneous Domains for Accelerating Hydrogen Evolution Reaction
Yu Qiu, Jinzheng Liu, Mengxiao Sun, Jifa Yang, Junzhe Liu, Xiaoyan Zhang*, Xuejun Liu* and Lixue Zhang*
Chin. J. Struct. Chem. 2022, 41, 2207040-2207045 DOI: 10.14102/j.cnki.0254-5861.2022-0144
July 18, 2022
hydrogen evolution reaction, water electrolysis, Co/MoN, heterogeneous domains
ABSTRACT
Developing efficient and durable electrocatalysts for water splitting, which has long been regarded as one of the most promising patterns to produce green hydrogen, is of great significance but still challenging. Herein, ample Co/MoN heterogeneous domains/nitrogen-doped carbon (Co/MoN/NC) nanosheet arrays as high-performance hydrogen evolution reaction (HER) electrocatalyst via a typical nitriding-carbonization strategy are successfully prepared on nickel foam (NF), which exhibits a low overpotential of 29 mV at 10 mA cm-2, together with excellent durability at 20 mA cm-2 for 90 h in alkaline solution. Such excellent catalytic property for HER can be attributed to the generation of abundant Co/MoN heterogeneous structures. Additionally, the high conductivity of Co/MoN and NC also increases the charge transfer rate, further helping accelerate the reaction rate of HER. This work presents an efficient method for improving the catalytic hydrogen evolution activity in basic solution. -
ArticleExplicating the Role of Metal Centers in Porphyrin-Based MOFs of PCN-222(M) for Electrochemical Reduction of CO2
Mengjie Liu, Mengting Peng, Baoxia Dong*, Yunlei Teng, Ligang Feng and Qiang Xu*
Chin. J. Struct. Chem. 2022, 41, 2207046-2207052 DOI: 10.14102/j.cnki.0254-5861.2022-0057
July 18, 2022
PCN-222, electrochemical reduction of CO2, DFT calculation, MOFs
ABSTRACT
The porphyrin-based MOFs formed by combining Zr6 clusters and porphyrin carboxylic acids with clear M-N4 active centers show unique advantages in electrocatalytic reduction of CO2 (CO2RR). However, its conductivity is still the bottleneck that limits its catalytic activity due to the electrical insulation of the Zr cluster. Therefore, the porphyrin-based MOFs of PCN-222(M) (M = Mn, Co, Ni, Zn) with explicit M-N4 coordination were combined with the highly conductive material carbon nanotube (CNT) for discussing the influence of metal centers on the CO2RR performance based on theoretical calculations and experimental observations. The results show that the PCN-222(Mn)/CNT, PCN-222(Co)/CNT, and PCN-222(Zn)/CNT all exhibit high selectivity to CO (FECO > 80%) in the range of -0.60 to -0.70 V vs. RHE. The FECOmax of PCN-222(Mn)/CNT (-0.60 V vs. RHE), PCN-222(Co)/CNT (-0.65 V vs. RHE), and PCN-222(Zn)/CNT (-0.70 V vs. RHE) are 88.5%, 89.3% and 92.5%, respectively. The high catalytic activity of PCN-222(Mn)/CNT and PCN-222(Co)/CNT comes from the excellent electron mobility of their porphyrin rings and their low ΔG*COOH (0.87 and 0.58 eV). It reveals that the strength of backbonding π of the transition metal and its influence on the electron mobility in the porphyrin ring can affect its CO2RR activity. -
ArticleHollow Fe4C/FeP Nanoboxes with Heterostructure and Carbon Armor for Efficient and Stable Hydrogen Evolution
Jing-Yi Xie, Hui-Ying Zhao, Yi-Wen Dong, Yang Wu, Da-Peng Liu*, Yong-Ming Chai and Bin Dong*
Chin. J. Struct. Chem. 2022, 41, 2207053-2207058 DOI: 10.14102/j.cnki.0254-5861.2022-0102
July 18, 2022
carbon armor, hollow box, heterostructured electrocatalysts, hydrogen evolution reaction
ABSTRACT
The heterojunction interfacial modulation of FeP is an effective strategy to regulate the intrinsic activity and stability, which is a major challenge to promote the industrial application of FeP-based electrocatalysts. Herein, hollow Fe4C/FeP box with heterojunction interface and carbon armor is successfully synthesized, which can expose numerous active sites and protect catalyst from corrosion. Electrochemical measurements show that Fe4C/FeP exhibits excellent hydrogen evolution activity and stability. It only needs 180 mV to achieve the current density of 10 mA cm-2. The high-activity may be due to the synergistic effects of porous framework, graphitic carbon coating and heterojunction structure of Fe4C and FeP, which optimize the electronic structure and accelerates electron transfer. In addition, the target catalyst can withstand 5000 cycles of CV testing without significant change in properties. The excellent stability may be attributed to the graphitic carbon coating as the armor that can prevent the catalyst from corrosion of electrolyte. This work may provide a synthetic approach to produce a series of carbon-coated and heterojunction structure of transition metal phosphides for water splitting. -
ArticleAcid-Stable CoWO4/WO3-Microrod Coated by a Thin Carbon-Layer as Efficient Pt Co-Catalysts for Methanol Oxidation and Oxygen Reduction
Jiahuan Li, Jiahao Xie, Xinyu Wang, Ying Dai*, Xiaoqin Xu, Jin Liu, Zhuang Cai*, Xin Meng and Jinlong Zou*
Chin. J. Struct. Chem. 2022, 41, 2207059-2207067 DOI: 10.14102/j.cnki.0254-5861.2022-0104
July 18, 2022
acid resistance, methanol-tolerance, oxygen vacancies, strong metal-support interaction, thin carbon-layer
ABSTRACT
Insufficient activity and instability (poisoning) of Pt-based electrocatalysts for methanol oxidation and oxygen reduction reactions (MOR/ORR) impede the development of direct methanol fuel cells. Here, CoWO4 nanoparticles-loaded WO3 microrods coated by a thin carbon-layer are used as Pt-supports/co-catalysts for MOR/ORR. WO3 grows along the (110) crystal plane to form microrod (diameter of ~0.6 um), which is coated by a carbon-layer (~5 nm). Pt-CoWO4/WO3@NCL-mr (850 ℃) shows a higher mass activity (2208 mA mg-1pt) than the commercial Pt/C (659.4 mA mg-1pt). CoWO4/WO3 heterojunction on the microrod surface with abundant oxygen vacancies allows the generation of surface-adsorbed hydroxyl to facilitate CO elimination and regeneration of the occupied Pt active-sites (promising stability). Pt-CoWO4/WO3@NCL-mr (850 ℃) has higher half-wave (0.46 V) and onset (0.54 V) potentials than Pt/C (0.41 and 0.50 V) for ORR. The microrod structure of CoWO4/WO3@NCL facilitates the dispersibility of Pt NPs to increase the utilization of Pt active sites and relieve the self-aggregation of Pt to obtain a promising synergy between Pt and CoWO4 (Co2+) for ORR in acid media. This study provides insights not only into the synthesis of acid-resistant WO3@NCL microrod as active Pt co-catalyst, but also into the effective utilization of surface oxygen vacancies and Co2+ for MOR/ORR. -
ArticleP-Ni4Mo Catalyst for Seawater Electrolysis with High Current Density and Durability
Gai Li, Suyang Feng, Jing Li*, Peilin Deng, Xinlong Tian, Chongtai Wang and Yingjie Hua*
Chin. J. Struct. Chem. 2022, 41, 2207068-2207073 DOI: 10.14102/j.cnki.0254-5861.2022-0110
July 18, 2022
seawater electrolysis, electrodeposition, hydrogen evolution reaction, phosphorus doping
ABSTRACT
Rational design of highly efficient and durable electrocatalysts with low cost to replace noble-metal based catalysts for seawater electrolysis is extremely desirable, but challenging. In this work, we demonstrate a rapid electrodeposition method by growing P-Ni4Mo on the surface of the copper foam (CF) substrate to synthesize an efficient seawater electrolysis catalyst (P-Ni4Mo/CF). The catalyst exhibited considerable HER performance and stability in alkaline seawater, with the overpotential as low as 260 mV at a current density of 100 mA cm-2. The P-Ni4Mo/CF is capable of achieving 1.0 A cm-2 with an overpotential of 551 mV, which is slightly worse than that of the Pt/C catalyst (453 mV). Moreover, P-Ni4Mo/CF demonstrates robust durability, with almost no activity loss after the durability test for more than 200 h. This work not only reports a new catalyst for seawater electrolysis, but also presents a strategy for the performance enhancement of seawater electrolysis. -
ArticleCoupling of NiFe-Based Metal-Organic Framework Nanosheet Arrays with Embedded Fe-Ni3S2 Clusters as Efficient Bifunctional Electrocatalysts for Overall Water Splitting
Xianbiao Hou, Tianyuan Jiang, Xiujuan Xu, Xingkun Wang, Jian Zhou, Huimin Xie, Zhicheng Liu, Lei Chu* and Minghua Huang*
Chin. J. Struct. Chem. 2022, 41, 2207074-2207080 DOI: 10.14102/j.cnki.0254-5861.2022-0145
July 18, 2022
metal-organic frameworks, metal sulfides, nanosheet arrays, electrocatalysts, water splitting
ABSTRACT
Developing highly efficient, easy-to-make and cost-effective bifunctional electrocatalysts for water splitting with lower cell voltages is crucial to producing massive hydrogen fuel. In response, the coupled hierarchical Ni/Fe-based MOF nanosheet arrays with embedded metal sulfide nanoclusters onto nickel foam skeleton (denoted as Fe-Ni3S2 @NiFe-MOF/NF) are fabricated, in which the Fe-Ni3S2 clusters could effectively restrain the aggregation of the layer metal-organic frameworks (MOF) nanosheets and adjust the local electronic structures of MOFs nanosheets. Benefiting from the rapid charge transfer and the exposure of abundant active sites, the well-designed Fe-Ni3S2@NiFe-MOF/NF displays excellent oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance. More importantly, when equipped in the alkaline water electrolyzer, the Fe-Ni3S2@NiFe-MOF/NF enables the system with a mere 1.6 V for achieving the current density of 10 mA cm-2. This work offers a paradigm for designing efficient bifunctional HER/OER electrocatalysts based on the hybrid materials of nanostructured metal sulfide and MOF.
- Address: Fuzhou High & New Technology Industrial Zone, Shangjie, Minhou, Fuzhou, Fujian 350108, China
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- E-mail: cjsc@fjirsm.ac.cn