Journal of Materials Chemistry A
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2021
·Vol. 10
·期 11
·6007-6015
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IF 12.732
Min Li,Minmin Wang,Dongyuan Liu,Yuan Pan,Shoujie Liu,Kaian Sun,Yanju Chen,Houyu Zhu,Wenyue Guo,Yanpeng Li,Zhiming Cui,Bin Liu,Yunqi Liu,Chenguang Liu
Single-atom catalysts (SACs) regulated by heteroatoms have displayed great potential as electrocatalysts for highly efficient hydrogen evolution reaction (HER); however, the controllable synthesis of an axial coordination structure of SACs to achieve robust HER performance remains a great challenge. Herein, we have proposed a doping-adsorption-pyrolysis strategy to construct NiN4–Cl active sites with axial Cl coordination for accelerating electrocatalytic HER. The obtained NiN4–Cl SAs/NC catalyst exhibits superior HER activity with low over-potential, small Tafel slope, high turnover frequency, and long-term stability. Density functional theory calculation reveals that the excellent HER performance of NiN4–Cl SAs/NC originates from the axial Cl-coordination-induced electronic localization enhancement, which is beneficial for the adsorption and activation of H* intermediate, thus accelerating the HER process. This work opens a new opportunity for rational design and construction of high-performance SAC catalysts by axial coordination strategy for electrocatalytic application.
研究领域:
材料科学
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电催化
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2019
·Vol. 29
·期 10
·1806884
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IF 15.621
Chenbao Lu,Jian Yang,Shice Wei,Shuai Bi,Ying Xia,Mingxi Chen,Yang Hou,Ming Qiu,Chris Yuan,Yuezeng Su,Fan Zhang,Haiwei Liang,Xiaodong Zhuang
Electrochemically driven carbon dioxide (CO 2 ) conversion is an emerging research field due to the global warming and energy crisis. Carbon monoxide (CO) is one key product during electroreduction of CO 2 ; however, this reduction process suffers from tardy kinetics due to low local concentration of CO 2 on a catalyst's surface and low density of active sites. Herein, presented is a combination of experimental and theoretical validation of a Ni porphyrin-based covalent triazine framework (NiPor-CTF) with atomically dispersed NiN 4 centers as an efficient electrocatalyst for CO 2 reduction reaction (CO 2 RR). The high density and atomically distributed NiN 4 centers are confirmed by aberration-corrected high-angle annular dark field scanning transmission electron microscopy and extended X-ray absorption fine structure. As a result, NiPor-CTF exhibits high selectivity toward CO 2 RR with a Faradaic efficiency of >90% over the range from −0.6 to −0.9 V for CO conversion and achieves a maximum Faradaic efficiency of 97% at −0.9 V with a high current density of 52.9 mA cm −2 , as well as good long-term stability. Further calculation by the density functional theory method reveals that the kinetic energy barriers decreasing for *CO 2 transition to *COOH on NiN 4 active sites boosts the performance.
研究领域:
材料科学
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催化化学
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环境科学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Huan Wang,Shu-Wei Yin,Jianchuan Liu,Weitao Wang,Zhen-Hong He,Kuan Wang,Zhi-Hao Zhao,Zhao-Tie Liu
Ni, especially Ni single atom catalysts (SACs) are the most promising electrocatalyst in the reduction of CO 2 to CO. However, the high energy barrier for the formation of *COOH on Ni SA sites leads to a high overpotential for CO 2 RR, which severely hinders the CO production efficiency. How the coupling effect of Ni SAs and Ni nanoparticles (NPs) sites improve the performance of Ni-based electrocatalysts is interesting to be investigated. Herein, theoretical calculations revealed that the synergy of Ni SAs and Ni NPs could efficiently lower the energy barrier of the *COOH formation via promoting the H 2 O dissociation process to accelerate the *H supply for CO 2 protonation as well as promote the CO 2 adsorption and CO desorption, thus improving catalytic activity. Based on the theoretical study, Ni-N 4 SA coupled with Ni nanoparticles supported on nitrogen-doped carbon nanotubes (Ni-N 4 Ni NP /NCNT) was designed. As electrocatalyst, the Ni-N 4 Ni NP /NCNT showed an ultralow onset overpotential of 60 mV for CO 2 RR-to-CO, and achieves a FE CO of ∼99 % from an overpotential of as low as 160 mV, outperforming state-of-the-art Ni SACs. This work not only sheds new light for the rational synthesis of Ni-based catalysts with both Ni SAs and Ni NPs sites to achieve efficient CO 2 RR to CO, but also offers an in-depth insight for the origin of efficient performance of cooperative Ni SA -Ni NP catalysts.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2024
·
IF 15.7
Yuan Jiang,Ji Yang,Mu-Lin Li,Xue-Jia Wang,Na Yang,Wei-Ping Chen,Jin-Chao Dong,Jian-Feng Li
ABSTRACT Metal-nitrogen-carbon single-atom catalysts (M-N-C SACs) have emerged as a highly promising material for ammonia synthesis from electrocatalytic nitrate reduction due to their isolated metal site and capacity to prevent the N–N coupling. However, understanding the structure-activity relationship at molecular level remains challenging because of the inhomogeneous M N x structure presented in current synthesized M-N-C catalysts. In this study, we utilized metal phthalocyanine ( M Pc) as a model platform catalyst containing a uniform and well-defined M N 4 center to unravel their intrinsic activity tendency toward ammonia synthesis from nitrate reduction, both experimentally and theoretically. Our experimental results exhibit a significant activity difference for ammonia production in the order of FeN 4 > CuN 4 > NiN 4 > MnN 4 > CoN 4 > ZnN 4 , and among which the FeN 4 site delivers much higher faradic efficiency and the highest turnover frequency of 83.3% and 4395.2 h –1 at –1.0 V vs . RHE, respectively. Density-functional theory calculations indicates that, compared to CoN 4 and MnN 4 , the FeN 4 site not only has appropriate adsorption strength for NO x intermediate species, but also has certain inhibitory effects on hydrogen evolution reaction process. These findings provide systematic and reliable guidance for catalyst synthesis toward nitrate reduction to NH 3 from both the experimental and computational perspectives.
研究领域:
催化
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电化学
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材料科学
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理论化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）