电催化还原氮制氨的最新进展

氮还原反应在生态系统、农业系统和工业氮循环中发挥着至关重要的作用.然而,由于氮气在水中的溶解度低,N≡N三键结构稳定,且存在与析氢反应的激烈竞争,因此目前电化学氮还原反应面临着产率缓慢、法拉第效率低等挑战.尽管研究者们通过不懈的努力已经在该领域取得了显著的进展,但距离其实际应用仍有较大差距.因此,如何通过多方面的调控手段,尽早实现人工固氮的工业化生产,成为当前该领域亟待解决的关键问题.本文系统梳理了电催化还原氮制氨的最新进展.首先,对NRR的机理进行了全面介绍.详细介绍了五种备受关注的氮还原机理:解离机理、结合机理、交替机理、酶促机理以及最新发现的马尔斯-范克雷维伦机理.通过对比电催化氮还原与哈珀法催化氮还原的反应机理,阐明了电催化氮还原的优势.然后,总结了该领域最新的研究进展.详细介绍了高性能氮还原催化剂的最新设计开发成果,基于近五年的相关报道,重点介绍了Mo基催化剂、Cu基催化剂、Ru基催化剂、Bi基催化剂和Fe基催化剂的研究进展.此外,对其他过渡金属基催化剂和非金属催化剂也进行了评述和展望,并对不同催化剂的优缺点进行了系统的比较.随后,对新型氮还原反应装置的研究进展进行了综述.讨论了新型反应器对缓解氮分子低溶解度这一问题的关键作用,强调了研发新型氮还原反应装置对提升电催化氮还原性能的重要性.在NRR反应路径的调控和优化方面,本文总结了最新的研究成果,特别是Li介导的氮还原反应的重要意义,证实了反应路径的调控优化是提升氮还原性能的有效手段.更为重要的是,从目前最新的研究成果出发,提出了氮还原性能的提升需要多方面的协同调控,单一的优化手段难以突破现有的瓶颈,这为后续的研究提供了重要参考.在展望部分,强调了氮还原领域目前面临的挑战并讨论了未来的研究方向.综上,本文系统地总结了近年来的研究进展,包括高性能催化剂、新型反应设备以及氮还原反应路径的调控和优化.提升氮还原反应的整体性能需要多方面的协调调控,仅关注催化剂很难取得重大突破.本文旨在为氮还原催化剂和反应器的设计以及反应路径的调控优化提供参考.

Rational design of MXene-based vacancy-confined single-atom catalyst for efficient oxygen evolution reaction

Two-dimensional transition metal carbides(MXenes) have been demonstrated to be promising supports for single-atom catalysts(SACs) to enable efficient oxygen evolution reaction(OER).However,the rational design of MXene-based SACs depends on an experimental trial-and-error approach.A theoretical guidance principle is highly expected for the efficient evaluation of MXene-based SACs.Herein,highthroughput screening was performed through first-principles calculations and machine learning techniques.Ti_(3)C_(2)(OH)_(x),V_(3)C_(2)(OH)_(x),Zr_(3)C_(2)(OH)_(x),Nb_(3)C_(2)(OH)_(x),Hf_(3)C_(2)(OH)_(x),Ta_(3)C_(2)(OH)_(x),and W_(3)C_(2)(OH)_(x) were screened out based on their excellent stability.Zn,Pd,Ag,Cd,Au,and Hg were proposed to be promising single atoms anchored in MXenes based on cohesive energy analysis.Hf_(3)C_(2)(OH)_(x) with a Pd single atom delivers a theoretical overpotential of 81 mV.Both moderate electron-deficient state and high covalency of metal-carbon bonds were critical features for the high OER reactivity.This principle is expected to be a promising approach to the rational design of OER catalysts for metal-air batteries,fuel cells,and other OER-based energy storage devices.

Expediting^(*)OH accumulation kinetics on metal-organic frameworks-derived CoOOH with CeO_(2) “accelerator” for electrocatalytic 5-hydroxymethylfurfural oxidation valorization

In this work,nickel foam supported CeO_(2)-modified CoBDC(BDC stands for terephthalic acid linker)metal-organic frameworks(NF/CoBDC@CeO_(2)) are prepared by hydrothermal and subsequent impregnation methods,which can be further transformed to NF/CoOOH@CeO_(2) by reconstruction during the electrocatalytic test.The obtained NF/CoOOH@CeO_(2) exhibits excellent performance in electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF) because the introduction of CeO_(2) can optimize the electronic structure of the heterointerface and accelerate the accumulation of ^(*)OH.It requires only a potential of 1.290 V_(RHE) to provide a current density of 50 mA cm^(-2) in 1.0 M KOH+50 mM HMF,which is 222 mV lower than that required in 1,0 M KOH(1.512 V_(RHE)).In addition,density-functional theory calculation results demonstrate that CeO_(2) biases the electrons to the CoOOH side at the heterointerface and promotes the adsorption of ^(*)OH and ^(*)HMF on the catalyst surface,which lower the reaction energy barrier and facilitate the electrocata lytic oxidation process.

High-throughput calculation-based rational design of Fe-doped MoS_(2) nanosheets for electrocatalytic p H-universal overall water splitting

Electrocatalytic water splitting is crucial for H2generation via hydrogen evolution reaction(HER)but subject to the sluggish dynamics of oxygen evolution reaction(OER).In this work,single Fe atomdoped MoS_(2)nanosheets(SFe-DMNs)were prepared based on the high-throughput density functional theory(DFT)calculation screening.Due to the synergistic effect between Fe atom and MoS_(2)and optimized intermediate binding energy,the SFe-DMNs could deliver outstanding activity for both HER and OER.When assembled into a two-electrode electrolytic cell,the SFe-DMNs could achieve the current density of 50 mA cm^(-2)at a low cell voltage of 1.55 V under neutral condition.These results not only confirmed the effectiveness of high-throughput screening,but also revealed the excellent activity and thus the potential applications in fuel cells of SFe-DMNs.

Bidentate carboxylate linked TiO2 with NH2-MIL-101(Fe)photocatalyst:a conjugation effect platform for high photocatalytic activity under visible light irradiation

Interfacial conjugation was employed to engineering preparation of TiO2@NH2-MIL-101(Fe)heterojunction photocataysts through carboxylate bidentate linkage with TiO2 and NH2-MIL-101(Fe),which can enhance the electron transfer capability from metal-organic frameworks(MOFs)to TiO2 and photocatalytic activity.The carbon nanospheres derived from glucose act as reducing agent and template to synthesize oxygen vacancies TiO2 hollow nanospheres.Then,the oxygen vacancies were employed as antennas to connect 2-aminoterephtalic acid as bidentate carboxylate chelating linkage on TiO2,which have been proved by the density functional theory(DFT)calculations.Subsequently,NH2-MIL-101(Fe)was coordinatingly formed on the surface of TiO2.The conjugation effects between TiO2 and NH2-MIL-101(Fe)enhanced the electron transfer capability and could also induce the band tail states to narrow bandgap of the composites.Thus,the photodegradability of methylene blue was remarkably enhanced under visible light irradiation.The degradation rate of TiO2@17%NH2-MIL-101(Fe)was 0.131 min-1,which was about 3.5 and 65 times higher than that of NH2-MIL-101(Fe)and TiO2,respectively.

Covalent-organic frameworks with keto-enol tautomerism for efficient photocatalytic oxidative coupling of amines to imines under visible light

Photocatalytic oxidation of organic molecules into highly value-added products is an innovative and challenging research which has gradually attracted remarkable attention of scientists.In this work,it is demonstrated that the COF-TpPa with keto-enol tautomerism equilibrium structure shows excellent performance(yield>99%after 8 h)in the selective photocatalytic oxidative coupling of amines to imines under visible light irradiation.It is revealed that three kinds of reactive oxygen species(superoxide radical,hydroxyl radical and singlet oxygen)participate in this photocatalytic oxidation reaction.In addition,hydrogen protons cleaved from the benzyl are proven to be reduced to hydrogen in the conduction band of COF-TpPa in anaerobic atmosphere,accompanied with the formation of imines.The direct hydrogen evolution from amine provides an effective way to extract clean energy from organic molecule as well as the production of value-added chemicals.As a contrast,COF-LZU1 with similar structure and chemical composition to COF-TpPa but without keto-enol tautomerism exhibits worse optical properties and photocatalytic performance.It is also demonstrated that keto-enol tautomerism favors the adsorption of benzylamine based on the characterization results and theoretical calculations.