具有光控氧空缺的钼掺杂Bi5O7Br纳米片用于光催化氮气合成氨

氨(NH3)作为合成燃料、化肥和潜在能源载体的重要前体,是现代化学工业中最重要的化学品之一.工业中主要通过高能耗的Haber-Bosch工艺在高温高压下将氮气和氢气转化为NH3,而原料氢气由天然气蒸汽获得,因而不仅消耗大量能源,而且导致温室气体二氧化碳的大量排放,对环境造成危害.光催化固氮以光能为驱动力,以水为质子源,为合成NH3提供了一种温和、绿色和可持续的方法.然而,传统固氮催化剂具有与N2结合弱、成键难以及电子转移效率低的缺点.为了克服上述问题,在催化剂中引入氧空缺和过渡金属作为给电子中心和活性位点的策略被广泛研究.本文以半导体Bi5O7Br纳米片作为研究对象,通过在水热合成过程中添加Na2MoO4前驱盐在Bi5O7Br中掺杂钼元素,合成了不同摩尔含量的钼掺杂Bi5O7Br(Mo-Bi5O7Br)纳米片,并将其应用于光催化N2还原反应,发现Mo-Bi5O7Br的光催化固氮性能显著优于空白Bi5O7Br的催化性能.扫描电镜、透射电镜、能量色散X射线元素映射以及X射线光电子能谱的结果表明,掺杂过程不会影响Bi5O7Br纳米片的晶相和形貌,掺杂后钼元素均匀地分布在Bi5O7Br纳米片晶格中.采用紫外可见漫反射光谱、电子自旋共振光谱、氮气程序升温脱附谱以及光电化学测试等方法研究了Mo-Bi5O7Br相较于空白Bi5O7Br纳米片在光催化N2还原反应中催化性能提升的原因.UV-vis DRS结果表明,钼掺杂对Bi5O7Br可见光吸收能力具有增强作用.以催化NH3产率最高的Mo-Bi5O7Br-1(Mo摩尔百分含量为1％)为研究样本,EPR结果表明,在黑暗条件下,只有Mo-Bi5O7Br-1样品可以检测到明显的表面氧空位(OVs)信号;在光照条件下,Bi5O7Br和Mo-Bi5O7Br-1两种样品都出现OVs的信号峰,但同等光照时间下的Mo-Bi5O7Br-1具有更高的信号强度.此外,OVs信号会随着光照时间的延长逐渐增强;当移除光源后,信号强度逐渐降低.这表明Mo-Bi5O7Br-1在光照下会产生更高浓度的表面光控OVs.N2-TPD结果表明,光控OVs作为活性位点促进催化剂对N2的吸附.关闭光源后,OVs被环境中的水或氧气中的氧原子重新填充,避免了OVs易被氧化而导致反应失活的缺点,有助于保持Mo-Bi5O7Br-1催化N2还原反应的活性和稳定性.光电化学表征结果表明,Mo-Bi5O7Br-1中的光生载流子的分离和迁移效率明显提高.以上结果表明,掺杂过渡金属钼有助于Bi5O7Br纳米片表面光控OVs的生成,光控OVs作为活性位点提升了Bi5O7Br吸附和活化N2的能力,钼掺杂和光控OVs协同提高Bi5O7Br内部光生载流子的分离迁移效率,增强Bi5O7Br光催化固氮合成氨的反应性能.     

Mo的引入方式对CeO2脱硝性能的影响

固定源排放的氮氧化物(NOx)导致了严重的环境污染问题,NH3选择性催化还原(NH3-SCR)被认为是目前控制NOx排放的最有效技术,已广泛应用于电力行业的烟气排放治理.然而,我国非电行业的NOx减排仍然面临着重大挑战,因为其排放的废气温度通常低于300oC,且含有一定量的SO2,传统的钒基SCR催化剂因活性温度(300～400oC)较高而无法有效发挥作用.因此,亟待开发新型的高效低温SCR催化剂.铈基催化剂由于氧化铈(CeO2)的优异储氧能力(OSC)和良好的氧化还原能力而显示出较好的低温(80～300oC)脱硝性能,如Mn-Ce,W-Ce,Ta-Ce,Cu-Ce和Nb-Ce等.但这些铈基催化剂易被烟气中的SO2毒化而导致催化活性降低.因此,提高铈基SCR催化剂抗硫中毒能力是其产业化应用的关键.已有研究发现,通过构筑结构保护层或添加另一种金属来保护活性组分是提高SCR催化剂抗硫性能的一种可行策略.氧化钼(MoO3)通常被用做传统V2O5/TiO2催化剂的促进剂以提高其水热稳定性和表面酸性.研究表明,在V/Ti催化剂中引入钼物种不仅可以提高其SCR活性,而且提高了V/Ti催化剂的抗SO2性能,这是由于VMo/Ti表面较少的V–O–V键削弱了对SO2的氧化作用.Tang等开发了一种Fe2O3/MoO3纳米片催化剂,显示出比纯Fe2O3更好的抗SO2能力,主要是由于层状结构的MoO3能阻止NH4+在硫酸氢铵中的沉积.目前关于Mo的引入方式即催化剂的制备方法对铈基催化剂物化性能和NH3-SCR催化性能(特别是抗SO2能力)的影响的研究还比较少.本文分别采用浸渍法和沉淀法在CeO2中引入钼物种,制备了Mo-CeO2和MoCe-cp催化剂来探究制备方法对MoCe催化剂的脱硝性能及抗SO2中毒能力的影响.结果表明,引入Mo可以显著地提高CeO2的低温脱硝性能,其中Mo-CeO2催化剂在150 oC即可达到80％以上的脱硝效率,同时抗SO2中毒性能也得到了显著提高.对催化剂结构、氧化还原能力、表面酸度和反应物分子的吸附脱附性质进行了表征,并与MoCe催化剂脱硝性能和抗硫性能相关联.结果表明,Mo-CeO2和MoCe-cp催化剂的物理化学性质和脱硝性能有明显区别.首先,Mo-CeO2中的钼物种主要存在于CeO2表面,而MoCe-cp中的钼物种主要存在于CeO2体相,其为Mo-CeO2表面带来大量的Br?nsted酸位并抑制了硝酸盐的吸附,促使NH3-SCR反应按照Eley-Rideal机理进行,进而表现出优于MoCe-cp的低温活性.其次,Mo-CeO2表面更多的Mo物种抑制了SO2的吸附,从而使Mo-CeO2表现出更好的抗SO2性能.本文为具有实际应用前景的铈基NH3-SCR催化剂的设计提供了参考.     

用于柴油车尾气消除反应(NH3-SCR)的八元环沸石分子筛研究进展

系统总结了作为柴油车尾气消除反应(NH₃-SCR)催化材料的八元环沸石分子筛(CHA, AEI, RTH)的研究进展, 讨论了不同方法合成的八元环沸石分子筛在NH₃-SCR反应中的性能差异, 并对未来八元环分子筛的发展趋势进行了展望.     

使用四乙基氢氧化铵作为有机模板剂和常规硅铝源直接合成SSZ-13沸石分子筛

使用四乙基氢氧化铵作为有机模板剂, 利用常规铝源和硅源而不需要高硅Y沸石作为起始原料, 同时加入适量的沸石晶种直接合成了SSZ-13沸石分子筛. 所合成的沸石产物结晶度好, 具有良好的水热稳定性, 并在氨选择性催化还原(NH₃-SCR)反应中显示出优异的催化性能, 为其在工业上广泛应用提供了可能.     

SO_4~(2-)功能化处理对Fe_2O_3催化剂上氨选择性催化还原NO_x性能的促进机理研究

采用沉淀法制备了Fe(OH)_3和Fe_2O_3。通过硫酸化处理得到SO_4~(2-)/Fe(OH)_3和SO_4~(2-)/Fe_2O_3两种催化剂,并将其应用于氨选择性催化还原NO_x(NH_3-SCR)反应,研究了SO_4~(2-)功能化处理对Fe_2O_3催化剂上NH_3-SCR脱硝性能的促进机理。结果表明,与纯的Fe_2O_3相比,硫酸化处理得到的催化剂上SCR活性得到显著提升;其中,SO_4~(2-)/Fe(OH)_3表现出更加优异的催化性能,在250-450℃时NO_x转化率高于80%,且具有优异的稳定性和抗H_2O+SO_2性能。XRD、Raman、TG、FT-IR、H_2-TPR、NH_3-TPD和in situ DRIFTS等表征结果显示,硫酸功能化处理能抑制Fe_2O_3的晶粒生长,同时SO_4~(2-)与Fe~(3+)结合形成硫酸盐复合物,提高了催化剂表面酸性位点的数量和酸强度,抑制了Fe_2O_3上的氨氧化反应,从而提高了其脱硝催化性能。     

UTSA-280的氨改性以及C2H4/C2H6分离性能研究

炼厂干气中回收乙烯是扩宽C₂H₄来源的有效途径,但C₂H₄和C₂H₆物理性质和分子尺寸非常接近,分离困难.金属有机骨架材料（MOFs）近年来在低碳烃分离领域展现出广阔的前景.本工作采用氨吸附改性调节UTSA-280的结构,通过一维直孔道大小的调节实现C₂H₄/C₂H₆的高效分离.改性后的UTSA-280具有独特的超微孔结构能提升C₂H₄的吸附,而完全不吸附稍大的C₂H₆,实现理想的C₂H₄/C₂H₆吸附选择性（>1000）.结果表明,改性后的UTSA-280的C₂H₄吸附量可提高至2.83 mmol/g,与未改性的材料相比增加29%,并且能阻挡C₂H₆的吸附,最终达到>1200的C₂H₄/C₂H₆选择性.蒙特卡罗分子模拟（GCMC）计算C₂H₄/C₂H₆混合气体（1：1）的吸附得出,改性后UTSA-280孔内的C₂H₄吸附相比于C₂H₆具有更多的吸附分布.通过C₂H₄/C₂H₆混合气体穿透实验测试,改性后的UTSA-280材料能展现出48 min以上的分离时间,相比于未改性的材料,分离性能提升近1倍.     

Recent Progress on 2D Transition Metal Compounds-based Electrocatalysts for Efficient Nitrogen Reduction

Ammonia is a commodity chemical with high added value. Electrochemical reduction of nitrogen has great promise for the sustainable synthesis of ammonia in recent years. Because of its rich resources and unique electronic structure and characteristics, 2D transition metal compounds have been used as electrocatalysts for electrochemical reduction of nitrogen for clean and sustainable production of ammonia. This review outlines the latest development in the use of 2D transition metal compounds as high-efficiency electrocatalysts for nitrogen reduction reaction(NRR). First, we introduce the N₂ reduction mechanism, and briefly summarize the performance indicators of the catalyst. Then, we focused on the functionalization of unique 2D materials to design high-performance 2D electrocatalysts in respect of simulation calculation and experimental development. Finally, the current challenges and future opportunities for NRR electrocatalysts are introduced.     

Synthesis of N-TiO2@NH2-MIL-88(Fe) Core-shell Structure for Efficient Fenton Effect Assisted Methylene Blue Degradation Under Visible Light

Core-shell TiO₂-based photocatalysts with specific composition, morphology, and functionality have attracted considerable attention for their excellent degradation properties on organic pollutants via a photocatalytic oxidation process. Herein, a N-TiO₂@NH₂-MIL-88(Fe) core-shell structure was prepared by coating NH₂-MIL-88(Fe) on nitrogen-doped TiO₂(N-TiO₂) nanoparticles. Introduction of heteroatom nitrogen to pure TiO₂ expands the spectral response range, leading to enhanced quantum efficiency of photocatalyst. Furthermore, loading NH₂-MIL-88(Fe) on N-TiO₂ improved the adsorption ability of the nanocomposites due to the porous tunnels of NH₂-MIL-88(Fe). The resulted core-shell N-TiO₂@NH₂-MIL-88(Fe) nanocomposites realized the transfer of photo excited electrons from N-TiO₂ to NH₂-MIL-88(Fe) rapidly, partially reduced Fe³⁺ to Fe²⁺ in NH₂-MIL-88(Fe), and further enhanced the Fenton effect on efficiently degrading methylene blue dye(MB) under visible light(λ ≥ 420 nm) with the assistance of H₂O₂.     

Self-Assembly of DNA and RNA Building Blocks Explored by Nitrogen-14 NMR Crystallography: Structure and Dynamics

The isotopic enrichment of nucleic acids with nitrogen-15 is often carried out by solid-phase synthesis of oligonucleotides using phosphoramidite precursors that are synthetically demanding and expensive. These synthetic challenges, combined with the overlap of chemical shifts, explain the lag of nitrogen-15 NMR studies of nucleic acids behind those of proteins. For the structural characterization of DNA and RNA-related systems, new NMR methods that exploit the naturally occurring 99.9 % abundant nitrogen-14 isotope are therefore highly desirable. In this study, we have investigated nitrogen-14 spectra of self-assembled quartets based on the nucleobase guanine in the solid state by means of magic-angle spinning NMR spectroscopy. The network of dipolar proton–nitrogen couplings between neighboring stacked purine units is probed by 2D spectra based on ¹H→¹⁴N→¹H double cross-polarization. Interplane dipolar contacts are identified between the stacked G quartets. The assignment is supported by density functional theory (DFT) calculations of the anisotropic chemical shifts and quadrupolar parameters. The experimental spectra are fully consistent with internuclear distances obtained in silico. Averaging of chemical shifts due to internal motions can be interpreted by semiempirical calculations. This method can easily be extended to synthetic G quartets based on nucleobase or nucleoside analogs and potentially to oligonucleotides.     

Three-Component Reaction of Triphenylphosphine,Dimethyl Acetylenedicarboxylate,and Aldehyde Benzoylhydrazones: An Efficient One-Pot Synthesis of Stable Phosphorus Ylides

Protonation of the reactive 1:1 intermediate produced in the reaction between dimethyl acetylenedicarboxylate and triphenylphosphine by benzoylhydrazones leads to vinylphosphonium salts, which undergo Michael addition with the conjugate base of the NH acid to produce highly fanctionalized, salt-free phosphorus ylides in excellent yields.