ChemElectroChem
·
2023
·Vol. 10
·期 18
·e202300283
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IF 4
Yang Ming,Yidi Wang,Jiachuan Hua,Chang Liu,Jiashen Li,Bin Fei
Graphical A facile PVP assisted Zn 0.2 @ZIF-67 framework is thermally converted to micro-mesoporous carbon with abundant cobalt particles. Post phosphorus doping into carbon shells improves catalysts’ conductivity and modulates the electronic environment of Co element, facilitating efficient water splitting. The enhancement of electrocatalytic water splitting by modulating the intrinsic electronic environment of active sites has recently attracted lots of interest. Herein, cobalt-cobalt oxide (CoO x ) at carbons derived from metal-organic frameworks (Zn 0.2 @ZIF-67) have been modulated by using post-phosphine (P-CoO x /NCs), acid leaching (Co/NCs), and oxidation (O−CoO x /NCs) treatments. With the assistance of polyvinyl pyrrolidone, the resultant carbons obtain a high surface area (645.7 m 2 g −1 ) as well as a micro-/mesoporous system after carbonization at 920 °C. These advantages not only enhance the catalytic performance of catalysts, but also facilitate the charge transfer between interfaces towards the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). As a result, the constructed water splitting cell fabricated with 900P-CoO x /NCs requires a low overpotential (89 mV and 343 mV vs. reservable hydrogen electrode respectively) to drive HER and OER at 10 mA cm −2 , a low cell voltage (1.69 V), and a high stability with only 4.9 % decay after 15 hours operation in the alkaline medium.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2025
·
IF 3
Zhao Sirui,Zhou Heng,Cao Dengfeng,Sheng Beibei,Qian Fangren,Liu Chongjing,Chu Yongheng,Li Rongyao,Song Li,Chen Shuangming
Electrocatalytic reduction reaction of carbon dioxide (CO 2 RR) to formic acid is widely considered an effective strategy for addressing the greenhouse effect and enhancing energy conversion efficiency. However, existing catalytic systems are severely hampered by insufficient activity and significant hydrogen evolution reaction (HER), which substantially compromises the selectivity and stability of CO 2 RR, necessitating the development of highly efficient and stable electrocatalysts. Herein, we present a heteroatomic modification strategy to synthesize B-doped Bi and N-doped Bi electrocatalysts, and systematically investigate the regulation mechanism of incorporated elements on the electronic environment using X-ray absorption fine structure (XAFS) spectroscopy and other characterization techniques. The optimized B-doped Bi catalyst demonstrates exceptional catalytic performance, achieving a remarkable Faradaic efficiency of 95% for formic acid production at a high current density of −190 mA/cm 2 under alkaline conditions, while maintaining excellent stability for 20 h. Through comprehensive experimental characterization and theoretical calculations, we reveal that the B-doping-induced electron-rich structure significantly promotes CO 2 molecule activation and facilitates the formation of the key intermediate *OCHO, thereby achieving high selectivity and stability in CO 2 RR. This work not only elucidates the crucial role of electronic environment in CO 2 electrocatalytic conversion but also provides innovative insights into the rational design of high-performance electrocatalysts.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Kai Zhang,Rui Zhang,Yuxin Cui,Jiayin Shang,Xueling Wei,Sumin Wang,Siqin Jia,Ke Qin,Haiyan Zhang,Hongyan Wang,Taotao Ai,Qiguan Wang
The electrocatalytic nitrogen reduction reaction (NRR) to synthesize ammonia is an important and challenging task in chemistry, where low-cost, highly active non-metallic catalysts such as boron carbonitride (BCN) are still highly desired. Tuning the electronic environment of the active site B is an effective approach to improve the NRR performance of BCNs. However, the study on the mechanism of this effect has been seriously neglected. The diversity and controllability in atomic arrangements of BCN make it suitable for studying the relationship between the local chemical environment of boron and the catalytic properties. To this end, we design four kinds of BCN materials named as homogeneous BCN nanoribbon and BCN nanosheet enriched with B − C active sites and localized phase-separated BCN nanoribbon and BCN nanosheet rich in B − N active sites, and theoretically screen the homogeneous type BCN nanoribbons that have better NRR performances. Meanwhile, we experimentally demonstrate that the optimized charge redistribution of B atoms in BCN skeleton by tuning the electronic environment makes the B − C sites being the effective centers in NRR, and arising the excellent NH 3 productivity of 63.02 μg h −1 mg − 1 cat with a highest Faraday efficiency of 32.28 %.
研究领域:
化学
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材料科学
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电催化
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产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2019
·Vol. 149
·期 4
·974-984
·
IF 2.372
Zhang Xiaotong,He Ning,Liu Chunyan,Guo Hongchen
Highly dispersed Pt–Cu alloy nanoparticles encapsulated in silicalite-1 were prepared by one-pot method. Taking propane dehydrogenation as a probe reaction, it was found that anti-coke ability was improved by encapsulation. Through H 2 -TPR, CO adsorption DRIFT spectra and X-ray Photoelectron Spectroscopy experiment, enhanced anti-coke ability was ascribed to the electronic environment change of encapsulated metal. And it was further confirmed by in situ coking experiment. Owning to limited acidity, metal encapsulated by silicalite-1 molecular sieve exhibited better anti-coke ability and higher propylene selectivity than that by stronger acidic ZSM-5 molecular sieve. Moreover it was found that the combination of Cu and Pt made better catalytic performance and accelerated dehydrogenation more effectively compared with monometallic catalysts. Therefore, Pt–Cu alloy nanoparticles encapsulated in silicalite-1 molecular sieve core–shell material was a potential coke-resistant catalyst for alkane dehydrogenation reaction. Graphical Abstract
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Gaosheng Ren,Zhihui Su,Yu Tang,Weichen Du,Nan Xu,Chengyi Dai,Xiaoxun Ma
It is very important to design model catalysts to control the site distribution and develop methods to improve their electronic environment and thus promote the catalyst’s performance in the electrochemical reduction of CO 2 (CO 2 RR). In this work, a strategy of in-situ synthesis and anchoring of nanoparticles (SSAN) was developed. Using this strategy, a “jujube-cake” type catalyst was designed, referred to as Ag@4-MBA. In this catalyst, Ag nanoparticles (NPs) act as “jujube”, which are embedded in 4-mercaptobenzoic acid (4-MBA) acting as “cake”. A Pointer-shaped Ag@4-MBA material was prepared that achieved high loading of Ag species (∼24.0 wt%), high dispersion (5–10 nm), high CO mass activity (93.7 A g Ag −1 ), high CO faradaic efficiency (94.0%) and high CO production (2.0 mol g Ag −1 h −1 ), showing a superior performance to that of the recently reported Ag-based catalysts. Density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) characterization showed that a high degree of electron delocalization of the Ag–S–aromatic ring and reconstructing the electronic environment of the metal sites were achievied, it is beneficial to stabilize the reaction intermediate COOH*. This work provides a new approach for the design of metal nanoparticle model catalysts with more sustainable CO 2 RR.
研究领域:
材料科学
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催化化学
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环境科学
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产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 27
·14674-14681
·
IF 11.9
Huaikun Zhang,Wentao Wang,Zechuan Dai,Yin Zhu,Mingyu Cheng,Bocheng Zhang,Yafei Feng,Yangyang Zhang,Genqiang Zhang
Ru clusters have great potential as excellent bifunctional catalysts for the hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR), but suffer from the difficulty of stabilization on the substrate and tuning the electronic environment. Herein, we present Ru clusters supported on N, S co-doped hollow carbon spheres (Ru/NSCS) by elaborately designed Ru–S bonds to anchor Ru clusters and optimize the surrounding coordination environment. The Ru/NSCS exhibits superior electrocatalytic performance for the HER and HzOR, where an ultrasmall overpotential of 40 mV and a working potential of −81 mV at 10 mA cm−2 can be achieved, respectively. The two-electrode system requires an applied voltage of only 26 mV to achieve 10 mA cm−2 and remains stable for 20 hours. Theoretical calculations reveal that the Ru–S bonds induce partial charge transfer from Ru clusters to the N, S co-doped carbon base, thus optimizing the adsorption energy of *H and dehydrogenation intermediates of N2H4.
研究领域:
催化化学
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材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
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2025
·
IF 4.3
Fei Fan,Xiaodi Zhu,Jiacan Kang,Zhenyu Song,Jianwei Liu,Hailong Wang,Anning Zhou,Houxiang Sun,Zhiping Chen,Wenwu Zhou
Developing high-performance non-precious metal catalysts for liquid organic hydrogen storage is crucial for advancing hydrogen energy technologies. Herein, we proposed a strategy in which doped Ge promoters optimized electron environments of nGeNi active phase loaded on titanium-aluminum composite oxide support with highly ordered 2D hexagonal mesopores (nGeNi/TA, n = 0, 0.5, 1, and 2 wt%), successfully establishing electron-rich active phase with high matching to HOMO orbital of N-Ethylcarbazole (NEC) molecule. Meanwhile, both d-band center of active phase and electron densities of its conduction band were effectively adjusted. These improvements not only retained ability of nGeNi active phase to activate NEC and its intermediates, but also suitably weakened strong π-d interaction with their aromatic rings. Consequently, adsorption energy of each intermediate species was almost close to average energy of hydrogenation conversion stages, thereby decreasing desorption energy of complete hydrogenation product (12H). Compared with 0GeNi/TA catalyst, NEC conversion rate on the best 1GeNi/TA catalyst at low temperature (220℃) greatly increased by approximately 118 %, and 12H selectivity and its yield sharply improved by approximately 112 % and 132 %, respectively. Moreover, excessive accumulations of intermediate species were also effectively mitigated.
研究领域:
催化化学
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能源材料
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纳米材料
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表面科学
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氢能源技术
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yuqing Wang,Miao Jiang,Na Liu,Tian Tian,Changdao Li,Zhao Sun,Gewen Yu,Yanming Wang,Wenxiu He,Jian Ding,Li Yan,Yunjie Ding
Designing low-cost and highly efficient heterogeneous catalysts for olefin hydroformylation, particularly utilizing abundant internal olefins, represents a research area of considerable scientific and industrial significance. Herein, a series of N or P doped porous organic polymers (POPs-N&P) are designed and fabricated to serve as carriers by the solvothermal polymerization of vinyl functionalized amine-type N, pyridinic N, imidazole N and PPh 3 ligands. The microenvironments surrounding cobalt were effectively regulated in Co/POPs-N&P catalysts. Specifically, single atom Co/POPs-NPh 3 catalyst with amine-type N chemical configurations possesses superior olefins isomerization abilities, thereby presenting an excellent 2-octene conversion of 95.9 % with the oxygenates selectivity of 62.6 % and a turnover number of 561, outperforming most of heterogeneous cobalt-based catalysts reported to date. Experimental results verify that distinct electronic environment of Co sites lead to different olefins isomerization abilities. Abundant Co N active species are generated on the Co/POPs-NPh 3 catalyst, which are different with those active species produced on the Co/POPs-PPh 3 , Co/POPs-Im&DVB and Co/POPs-Py&DVB catalysts. Furthermore, a reaction mechanism was also suggested for 2-octene hydroformylation over the Co/POPs-NPh 3 catalyst. This work underlines the potential of POPs as an ideal platform for the modulation of the coordination environment of the Co sites toward improved hydroformylation of internal alkenes.
研究领域:
催化
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材料科学
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有机化学
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化学工程
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纳米技术
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
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IF 13.2
Hao Deng,Yang Li,Ruihua Chen,Chao Ma,Junpeng Jiang,Daoyang Han,Bingbing Fan,Hailong Wang,Rui Zhang,Gang Shao
The coordinated metal single-atoms (MSA) can significantly enhance the electromagnetic wave (EMW) absorption properties of materials through adjusting local electron structure and polarization relaxation. The symmetric electronic environments for EMW absorption have been extensively studied, but the asymmetric electron dispersion from an atomic-scale perspective is blurring puzzle. In this work, the amorphous polymer-derived SiZnCN ceramics with porous “Cheese” structure were prepared by regulating Zn coordination and pyrolysis temperature. The SiZnCN (15 wt% ZnAc doping) ceramics pyrolyzed at 1400 °C exhibits an effective absorption bandwidth (EAB) of 4.96 GHz at an ultrathin thickness of 1.28 mm. This SiZnCN ceramics after oxidized at 500 °C still possesses excellent high-temperature EMW absorption performance. Benefiting from the porous structure and coordinated single Zn atoms, the asymmetric electronic environment in amorphous SiZnCN ceramics is established, promoting electron/dipole and interfacial polarization. This work proposes an effective strategy to optimize electromagnetic wave absorption for high temperature by coordinating asymmetric electronic environments in disordered structures.
研究领域:
材料科学
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电磁功能材料
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陶瓷工程
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纳米材料
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介电性能
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）