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T. Koga 《Theoretical chemistry accounts》2005,113(3):183-186
In many-electron atoms, the average electron momentum p represents the mean momentum of a single electron when all the electron motions are averaged. If any two electrons are considered simultaneously, however, the average momentum p splits into two different momenta, low momentum p< and high momentum p>. For the 102 atoms He through Lr in their ground states, the momenta p< and p> are systematically examined at the Hartree–Fock limit level. It is also shown that the sum p>+p< and the difference p>–p< of the two momenta constitute upper and lower bounds to the electron-pair relative momentum p12=|p1–p2| and to the electron-pair center-of-mass momentum P=|p1+p2|/2. The tightness of the bounds is discussed for the 102 atoms. 相似文献
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Li Shiuan Ng Dr. Tharishinny Raja Mogan Jinn-Kye Lee Dr. Haitao Li Dr. Chi-Lik Ken Lee Prof. Hiang Kwee Lee 《Angewandte Chemie (International ed. in English)》2023,62(47):e202313695
The production of green hydrogen through photocatalytic water splitting is crucial for a sustainable hydrogen economy and chemical manufacturing. However, current approaches suffer from slow hydrogen production (<70 μmol ⋅ gcat−1 ⋅ h−1) due to the sluggish four-electrons oxygen evolution reaction (OER) and limited catalyst activity. Herein, we achieve efficient photocatalytic water splitting by exploiting a multifunctional interface between a nano-photocatalyst and metal–organic framework (MOF) layer. The functional interface plays two critical roles: (1) enriching electron density directly on photocatalyst surface to promote catalytic activity, and (2) delocalizing photogenerated holes into MOF to enhance OER. Our photocatalytic ensemble boosts hydrogen evolution by ≈100-fold over pristine photocatalyst and concurrently produces oxygen at ideal stoichiometric ratio, even without using sacrificial agents. Notably, this unique design attains superior hydrogen production (519 μmol ⋅ gcat−1 ⋅ h−1) and apparent quantum efficiency up to 13-fold and 8-fold better than emerging photocatalytic designs utilizing hole scavengers. Comprehensive investigations underscore the vital role of the interfacial design in generating high-energy photoelectrons on surface-degenerate photocatalyst to thermodynamically drive hydrogen evolution, while leveraging the nanoporous MOF scaffold as an effective photohole sink to enhance OER. Our interfacial approach creates vast opportunities for designing next-generation, multifunctional photocatalytic ensembles using reticular chemistry with diverse energy and environmental applications. 相似文献
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Jiahui Xian Suisheng Li Hui Su Peisen Liao Shihan Wang Runan Xiang Yawei Zhang Prof. Qinghua Liu Prof. Guangqin Li 《Angewandte Chemie (International ed. in English)》2023,62(30):e202306726
The conversion of industrial exhaust gases of nitrogen oxides into high-value products is significantly meaningful for global environment and human health. And green synthesis of amino acids is vital for biomedical research and sustainable development of mankind. Herein, we demonstrate an innovative approach for converting nitric oxide (NO) to a series of α-amino acids (over 13 kinds) through electrosynthesis with α-keto acids over self-standing carbon fiber membrane with CoFe alloy. The essential leucine exhibits a high yield of 115.4 μmol h−1 corresponding a Faradaic efficiency of 32.4 %, and gram yield of products can be obtained within 24 hours in lab as well as an ultra-long stability (>240 h) of the membrane catalyst, which could convert NO into NH2OH rapidly attacking α-keto acid and subsequent hydrogenation to form amino acid. In addition, this method is also suitable for other nitrogen sources including gaseous NO2 or liquidus NO3− and NO2−. Therefore, this work not only presents promising prospects for converting nitrogen oxides from exhaust gas and nitrate-laden waste water into high-value products, but also has significant implications for synthetizing amino acids in biomedical and catalytic science. 相似文献
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Xiaofang Bai Xiuping Zhang Yujiao Sun Mingcheng Huang Prof. Dr. Jiantao Fan Prof. Dr. Shaoyi Xu Prof. Dr. Hui Li 《Angewandte Chemie (International ed. in English)》2023,62(38):e202308704
To date, only a few noble metal oxides exhibit the required efficiency and stability as oxygen evolution reaction (OER) catalysts under the acidic, high-voltage conditions that exist during proton exchange membrane water electrolysis (PEMWE). The high cost and scarcity of these catalysts hinder the large-scale application of PEMWE. Here, we report a novel OER electrocatalyst for OER comprised of uniformly dispersed Ru clusters confined on boron carbon nitride (BCN) support. Compared to RuO2, our BCN-supported catalyst shows enhanced charge transfer. It displays a low overpotential of 164 mV at a current density of 10 mA cm−2, suggesting its excellent OER catalytic activity. This catalyst was able to operate continuously for over 12 h under acidic conditions, whereas RuO2 without any support fails in 1 h. Density functional theory (DFT) calculations confirm that the interaction between the N on BCN support and Ru clusters changes the adsorption capacity and reduces the OER energy barrier, which increases the electrocatalytic activity of Ru. 相似文献
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Yanmin Hu Tingting Chao Yapeng Li Peigen Liu Tonghui Zhao Ge Yu Cai Chen Xiao Liang Huile Jin Shuwen Niu Wei Chen Dingsheng Wang Yadong Li 《Angewandte Chemie (International ed. in English)》2023,62(35):e202308800
Water electrolysis for H2 production is restricted by the sluggish oxygen evolution reaction (OER). Using the thermodynamically more favorable hydrazine oxidation reaction (HzOR) to replace OER has attracted ever-growing attention. Herein, we report a twisted NiCoP nanowire array immobilized with Ru single atoms (Ru1−NiCoP) as superior bifunctional electrocatalyst toward both HzOR and hydrogen evolution reaction (HER), realizing an ultralow working potential of −60 mV and overpotential of 32 mV for a current density of 10 mA cm−2, respectively. Inspiringly, two-electrode electrolyzer based on overall hydrazine splitting (OHzS) demonstrates outstanding activity with a record-high current density of 522 mA cm−2 at cell voltage of 0.3 V. DFT calculations elucidate the cooperative Ni(Co)−Ru−P sites in Ru1−NiCoP optimize H* adsorption, and enhance adsorption of *N2H2 to significantly lower the energy barrier for hydrazine dehydrogenation. Moreover, a self-powered H2 production system utilizing OHzS device driven by direct hydrazine fuel cell (DHzFC) achieve a satisfactory rate of 24.0 mol h−1 m−2. 相似文献
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Yanan Chang Zhangyu Ma Xuyun Lu Shasha Wang Prof. Jianchun Bao Prof. Ying Liu Prof. Chao Ma 《Angewandte Chemie (International ed. in English)》2023,62(41):e202310163
The rational design of advanced nanohybrids (NHs) with optimized interface electronic environment and rapid reaction kinetics is pivotal to electrocatalytic schedule. Herein, we developed a multiple heterogeneous Co9S8/Co3S4/Cu2S nanoparticle in which Co3S4 germinates between Co9S8 and Cu2S. Using high-angle annular-dark-field imaging and theoretical calculation, it was found that the integration of Co9S8 and Cu2S tends to trigger the interface phase transition of Co9S8, leading to Co3S4 interlayer due to the low formation energy of Co3S4/Cu2S (−7.61 eV) than Co9S8/Cu2S (−5.86 eV). Such phase transition not only lowers the energy barrier of oxygen evolution reaction (OER, from 0.335 eV to 0.297 eV), but also increases charge carrier density (from 7.76×1014 to 2.09×1015 cm−3), and creates more active sites. Compared to Co9S8 and Cu2S, the Co9S8/Co3S4/Cu2S NHs also demonstrate notable photothermal effect that can heat the catalyst locally, offset the endothermic enthalpy change of OER, and promote carrier migrate, reaction intermediates adsorption/deprotonation to improve reaction kinetics. Profiting from these favorable factors, the Co9S8/Co3S4/Cu2S catalyst only requires an OER overpotential of 181 mV and overall water splitting cell voltage of 1.43 V to driven 10 mA cm−2 under the irradiation of near-infrared light, outperforming those without light irradiation and many reported Co-based catalysts. 相似文献
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光电催化水分解制氢是目前解决能源危机与环境污染最理想的技术之一.设计和构筑高效的光阳极是实现光电催化技术实际应用的关键.在众多半导体光阳极材料中,TiO_2纳米阵列由于其快的电荷传输速率,高的光热稳定性,无毒和成本低等优点,已经被广泛用于光电催化水分解反应的研究.但是TiO_2本征的光吸收范围窄、光生电荷复合率高、表面水氧化动力学缓慢严重地制约了其太阳能-氢能转换效率.我们结合近年来国内外及本课题组的研究工作详细论述了TiO_2纳米阵列的改性策略,主要包括利用元素掺杂来拓展TiO_2的光吸收范围并提高导电性,构筑异质结促进光电极电荷的分离与转移,半导体敏化增加光电极的可见光吸收并促进电荷转移,表面处理用于增加表面水氧化反应速率.最后指出了该材料发展现状,并对其发展前景做出展望.我们为进一步提高TiO_2纳米阵列的光电催化水分解活性提供了理论指导和实践借鉴. 相似文献
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