Ru和Cu助剂对费托合成Fe基催化剂反应性能的影响

研究了Ru和Cu助剂对无K的费托(F-T)合成Fe基催化剂的织构性质、物相结构、还原和碳化行为的影响.在n(H2)/n(CO)=2.0,t=260℃,P=1.5MPa和GHSV=2000h-1的条件下,采用固定床反应器考察了Ru,Cu助剂对Fe基催化剂费托合成反应性能的影响.采用低温N2物理吸附、X射线衍射、穆斯堡尔谱...     

氮掺杂碳纳米笼固载钌纳米粒子的费托合成性能

费托合成可以将来源广泛的合成气转化为低碳烯烃和燃油等高附加值化学品, 是后石油时代的重要化工过程, 而发展高性能的催化剂是该工程产业化的关键. 以具有高比表面积和高氮含量的氮掺杂碳纳米笼(NCNC)为载体, 采用等体积浸渍法制备了Ru的质量分数为20%的Ru/NCNC催化剂, 所得Ru纳米颗粒均匀分散, 相比于未掺杂碳纳米笼负载的Ru催化剂(Ru/CNC), Ru纳米粒子尺寸更小且分布更集中. Ru/NCNC催化剂展现出优异的费托合成催化性能, 在0.5 MPa和220 ℃的温和条件下, 具有高的催化活性、高的C₅₊选择性(55.7%)、低的CH₄选择性(13.5%)和高的催化稳定性(60 h, CO转化率保持在≈33%), 显著优于Ru/CNC. 这可归因于N掺杂提高了Ru活性中心的数量和电子态密度以及表面碱性, 增强了金属-载体相互作用, 进而提高Ru/NCNC的催化活性、长链产物(C₅₊)选择性、抗烧结能力和催化稳定性. 本研究提供了一条通过掺杂碳载体设计提升费托合成催化剂性能的有效策略.     

助剂对Co/Al2O3催化剂浆态床费托合成反应性能影响

考察了ZrO₂、Ru或Pt助剂对Co/Al₂O₃催化剂结构及浆态床费托合成反应性能的影响。实验结果表明,添加ZrO₂助剂可阻止或降低难还原铝酸钴的形成、促进催化剂的还原、提高Co/Al₂O₃催化剂对费托合成反应的催化活性、降低甲烷选择性并提高C₅₊烃选择性。H₂-TPR表征结果表明,少量Ru或Pt助剂均能降低Co-ZrO₂/Al₂O₃催化剂中钴物种还原温度(Co₃O₄→CoO和CoO→Co⁰),提高催化剂的还原度,催化剂呈现出良好的CO加氢反应活性。此外,催化剂组分间浸渍次序对费托合成反应性能有重要影响,载体γ-Al₂O₃先浸渍Zr组分,可有效抑制难还原化合物形成;Co、Ru组分共浸渍加强了Co和Ru组分密切接触程度,更利于钴物种的还原;Co、Pt组分依次浸渍更利于活性组分的均匀分布,催化剂具有最佳的费托合成反应性能。     

Ru助剂对Co/SiO2催化剂费托合成反应性能的影响

 考察了 Ru 助剂 (0.17%?9.96%) 对 Co/SiO2 催化剂结构及其费托合成反应性能的影响. 结果表明, Ru 助剂可降低 Co/SiO2 催化剂的还原温度, 从而提高其还原度. 光电子能谱和扩展 X 吸收射线精细结构研究表明, 即使 Ru 含量高达 9.96%, 在 Co/SiO2 催化剂焙烧过程中也未观察到 Ru 物种与 Co 物种作用形成的化合物. 还原后催化剂中 Ru 趋向于与 Co 物种紧密接触且分散在催化剂表面. H2 程序升温脱附结果表明, 随着 Ru 含量的增加, 位于反应温度附近的 H2 脱附峰面积增加, 即此时催化剂吸附 H2 能力提高, 因此反应活性单调增加, 但存在最佳 Ru 含量, 此时 C5+选择性最高.     

Ru助剂对Co/SiO_2/HZSM-5催化剂合成航空燃油类烃的影响

以中孔硅胶和微孔HZSM-5分子筛为复合载体,添加Ru制备了钴基催化剂,考察了Ru添加量(1%~4%,质量分数)对催化剂结构和固定床费托合成航空燃油类烃的影响。实验结果表明,制备的复合载体催化剂有一定的微孔和中孔结构,Ru的添加有利于Co分散,Ru促进的催化剂低温还原过程提高了催化剂在150~750℃的还原度和CO转化率,复合载体中HZSM-5分子筛利用其微孔结构,提高了异构烃的收率。当Ru负载量为1%时,CO转化率达到62.8%,航空燃油类烃的收率达到37.7%,包括约10.9%的异构烃。Ru负载量超过2%时,增强的催化剂CO加氢活性和CH4选择性,导致合成产物向低碳烃方向偏移。     

铁基催化剂在COx加氢制高附加值烃反应中的应用

化石燃料的广泛使用导致大气中CO₂的排放量急剧增加,进而引起全球变暖和海洋酸化等一系列问题.CO加氢(费托合成)反应是利用非石油来源的原料生产液体燃料和化学品的一种重要途径.同时,利用可再生的H₂将CO₂转化为高附加值的产品有利于减少对化石燃料的依赖,减轻由于大气中CO₂浓度过高带来的负面影响.开发新型、高效、稳定的催化剂是费托合成和CO₂加氢制高附加值烃的关键因素之一.Fe基、Co基和Ru基催化剂是费托合成中常用的催化剂.而在CO₂加氢反应中,Co基和Ru基催化剂上主要发生甲烷化反应,几乎没有长链烃生成.Fe基催化剂在费托合成和CO₂加氢反应中均表现出优异的催化生成长链烃性能.同时,Fe储量丰富和价格便宜的特点也促进Fe基催化剂在两个反应中的广泛应用.一般认为,在Fe基催化剂上CO₂通过逆水煤气变换反应生成CO,CO通过费托合成反应继续加氢生成烃类.因此,CO₂加氢反应和费托合成反应有相似之处,同时也有较大的区别.本文从活性相、助剂和载体的角度综述了各组分在Fe基催化剂催化CO/CO₂加氢反应中的作用,总结了其中的区别与联系.催化剂在反应中会发生复杂的相变过程,形成多种铁物种;其中,碳化铁(χ-Fe₅C₂,ε-Fe₂C,Fe₇C₃和θ-Fe₃C)在费托合成反应中是C-C偶联的活性相,但对于θ-Fe₃C现还存在一些争议.在CO₂加氢反应中Fe₃O₄催化逆水煤气变换反应,碳化铁催化CO加氢反应.金属助剂对CO/CO₂加氢反应的促进作用较为相似,在两个反应中碱金属的促进作用最为明显.费托合成反应对载体有较强的适应性,而CO₂加氢反应对载体敏感性较强,Al₂O₃,ZrO₂和碳材料载体效果较好.本文还总结了近些年来基于对活性相、助剂和载体的深入理解设计制备的一些新型催化剂及其在费托合成和CO₂加氢反应中的应用,包括具有新颖结构的催化剂、金属-有机骨架衍生催化剂以及与沸石分子筛结合的双功能催化剂.最后,还分析了目前Fe基催化剂在费托合成和CO₂加氢反应应用中所面临的问题和挑战,并对未来的发展趋势进行了展望.     

铁基催化剂在COx加氢制高附加值烃反应中的应用

化石燃料的广泛使用导致大气中CO₂的排放量急剧增加,进而引起全球变暖和海洋酸化等一系列问题.CO加氢(费托合成)反应是利用非石油来源的原料生产液体燃料和化学品的一种重要途径.同时,利用可再生的H₂将CO₂转化为高附加值的产品有利于减少对化石燃料的依赖,减轻由于大气中CO₂浓度过高带来的负面影响.开发新型、高效、稳定的催化剂是费托合成和CO₂加氢制高附加值烃的关键因素之一.Fe基、Co基和Ru基催化剂是费托合成中常用的催化剂.而在CO₂加氢反应中,Co基和Ru基催化剂上主要发生甲烷化反应,几乎没有长链烃生成.Fe基催化剂在费托合成和CO₂加氢反应中均表现出优异的催化生成长链烃性能.同时,Fe储量丰富和价格便宜的特点也促进Fe基催化剂在两个反应中的广泛应用.一般认为,在Fe基催化剂上CO₂通过逆水煤气变换反应生成CO,CO通过费托合成反应继续加氢生成烃类.因此,CO₂加氢反应和费托合成反应有相似之处,同时也有较大的区别.本文从活性相、助剂和载体的角度综述了各组分在Fe基催化剂催化CO/CO₂加氢反应中的作用,总结了其中的区别与联系.催化剂在反应中会发生复杂的相变过程,形成多种铁物种;其中,碳化铁(χ-Fe₅C₂,ε-Fe₂C,Fe₇C₃和θ-Fe₃C)在费托合成反应中是C-C偶联的活性相,但对于θ-Fe₃C现还存在一些争议.在CO₂加氢反应中Fe₃O₄催化逆水煤气变换反应,碳化铁催化CO加氢反应.金属助剂对CO/CO₂加氢反应的促进作用较为相似,在两个反应中碱金属的促进作用最为明显.费托合成反应对载体有较强的适应性,而CO₂加氢反应对载体敏感性较强,Al₂O₃,ZrO₂和碳材料载体效果较好.本文还总结了近些年来基于对活性相、助剂和载体的深入理解设计制备的一些新型催化剂及其在费托合成和CO₂加氢反应中的应用,包括具有新颖结构的催化剂、金属-有机骨架衍生催化剂以及与沸石分子筛结合的双功能催化剂.最后,还分析了目前Fe基催化剂在费托合成和CO₂加氢反应应用中所面临的问题和挑战,并对未来的发展趋势进行了展望.     

Cu、Ni、Ru、Pt对费托合成Fe催化剂的助剂作用研究

考察了Cu、Ni、Ru、Pt对费托合成Fe催化剂的助剂作用。XRD结果表明,加入Cu、Ni助剂对催化剂有一定的分散作用,而Ru、Pt影响不大。XPS结果表明,所有添加的助剂在催化剂表面均有一定程度的富集,且4种过渡金属助剂与Fe存在不同程度的电荷相互作用。H₂-TPR表明,Cu、Pt、Ru在催化剂还原过程中首先还原为金属态,进而能够明显促进催化剂的还原。CO-TPD表明,加入Cu、Pt、Ni助剂对CO的吸附活化有明显的促进作用。用固定床反应器对催化剂的费托反应性能进行了评价,反应结果表明,加入Ru、Ni、Pt、Cu会依次提高催化剂的反应活性,Pt、Cu、Ru、Ni助剂会依次使催化剂的CH₄选择性增加,并降低C₅₊的选择性。     

NiO/Ni纳米结构可见光驱动CO加氢制备高级烃类

正CO加氢高温高压制备高级烃类是一种重要的煤间接液化技术(又称费托反应),被认为是一种替代石油、实现煤碳能源洁净高附加值利用的重要途径,受到学术界和工业界的极大关注~1。常用的费托合成催化剂有Ru、Co、Fe基等催化剂~2。Ni基催化剂虽然被广泛应用于加氢化工反应,但是由于其C―C偶联效率低,趋于催化生成低值的甲烷,因此Ni基催化剂又被称为甲烷化催化剂~3。当前,基于费托反应发展一条清洁、绿色的新型能     

载体效应对Ru基催化剂费托合成制烯烃的性能影响（英文）

本研究考察了不同载体(CeO₂、ZrO₂、MnO₂、SiO₂和活性炭)对负载型Ru基费托合成制烯烃(FTO)催化剂结构和催化性能的影响。结果表明,载体的本征属性和金属-载体相互作用(MSI)对催化性能有很大影响。在同一反应条件下的催化活性关系为：Ru/SiO₂> Ru/ZrO₂> Ru/MnO₂> Ru/AC> Ru/CeO₂。对于烯烃选择性,Ru/SiO₂和Ru/MnO₂得到的总烯烃选择性最高,超过70%,而Ru/ZrO₂催化剂的烯烃选择性低至29.9%。由于金属Ru与SiO₂的金属载体相互作用较弱,反应后的Ru/SiO₂催化剂得到适中的Ru纳米颗粒尺寸(～5 nm)且反应活性也最高。对于Ru/AC和Ru/MnO₂,其Ru纳米颗粒尺寸仅为1-3 nm,表现出...     

充满生机和科学机遇的磷化学研究所

简要地综述了第十五届国际磷化学会议的报告内容，介绍了目前磷化学的主要 研究领域，包括不对称合成、配合化学，生物碱化学，药物化学，农业化学等相关 领域的研究动态及新进展。     

Exploring recent developments on 1,2,4-triazole: Synthesis and biological applications

Triazoles are nitrogen-bearing heterocycles. In the last few decades, researchers have focused on fused heterocycles, as they have better pharmacological effect compared to triazoles alone. Among the two isomers of triazole, this article aims to explore the work carried out on 1,2,4-triazole and N-bridged heterocycles derived from 1,2,4-triazole in last 18 years, highlight different synthetic pathways, and present a brief summary of the different biological activities possessed by 1,2,4-triazole derivatives. The information collected in this article is expected to help researchers to discover novel therapeutic agents for better applications in the field of pharmaceutical science.     

Novel arylpyridine‐based 1,3,4‐oxadiazoles: Synthesis,antibacterial, and anti‐inflammatory evaluation

In view of developing novel bioactive compounds, a series of 2‐(5‐[2‐methyl‐6‐arylpyridin‐3‐yl]‐1,3,4‐oxadiazol‐2‐ylthio)‐1‐arylethanones (6a–n) were designed and synthesized in good yield. Novel compounds were evaluated for their antibacterial and anti‐inflammatory activities. All synthesized compounds were screened for their antibacterial activity against Staphylococcus aureus, Bascillus subtilis, Eschericia coli, and Pseudomonas aeruginosa strains. Compounds 6a , 6b , 6c , 6h , and 6i displayed the highest antibacterial activity with minimal inhibitory concentration (MIC) values ranging from 6.25–12.5 μg/mL in comparison with the standard Ciprofloxacin. The results of anti‐inflammatory activity of carrageenan‐induced footpad edema assay indicated that tested compounds exhibited remarkable anti‐inflammatory activity with percentage of inhibition of 63.9–70.1% (potency 96.8–106.20% of indomethacin activity) after 3 hr. Particularly, 6c – e and 6j – l were found to be excellent inhibitors of inflammation, with potential higher than that of the standard, Indomethacin.     

Novel [1,2,4]triazolo[3,4-b][1,3,4]thiadiazine derivatives embedded with benzimidazole moiety as potent antioxidants

Fourteen novel [1,2,4]triazolo[3,4-b][1,3,4]thiadiazine derivatives bearing benzimidazole moiety ( 7a-n ) have been synthesized using the one-pot nitro reductive cyclization method. All the synthesized compounds were confirmed by ¹H nuclear magnetic resonance (¹H NMR), ¹³C NMR, fourier-transform infrared (FT-IR), mass spectrum, and elemental analyses. All the title compounds were subjected to in vitro antioxidant activity. The free radical scavenging activity of the compounds was examined using DPPH, nitric oxide, and superoxide radical scavenging methods. The results demonstrated that compound 3-(2-(3,4-dimethoxyphenyl)-1-propyl-1H-benzo[d]imidazol-5-yl)-6-4-tolyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine ( 7c ) was potent in scavenging both DPPH and nitric oxide radical with IC₅₀ values of 13.57 and 18.55 μg/ml when compared to the standard with IC₅₀ values of 23.75 and 23.14 μg/ml, respectively, which was due to the presence of electron-donating groups. The activity was found to decline when electron-donating groups were replaced by electron-withdrawing groups. Moderate scavenging activity was observed for the superoxide radical. Structure activity relationship and physiochemical properties were studied for all the derivatives.     

Dual zinc catalysts for L‐lactide polymerization and reaction of CO2 with cyclohexene oxide

A series of zinc complexes, [ L ^X ZnEt] ( 1–5 ) and [ L ^X Zn ₂ (OAc) ₃ ] (6–9) , associated with NNO‐tridentate Schiff base ligands (2‐(((2‐((cyclohexyl[methyl]amino)methyl)phenyl)imino)methyl)phenolate (CAP) derivatives), were synthesized, and their activity toward ring‐opening polymerization (ROP) of L‐lactide (LA) and the reaction of CO₂ with cyclohexene oxide were also investigated. All of [ L ^X ZnEt] revealed excellent catalytic activity to ring‐opening polymerization (ROP) of LA in the presence of benzyl alcohol. Among them, [ L ^H ZnEt] (1) showed the highest activity with 82% conversation within 45 s. In contrast, [L ^X Zn ₂ (OAc) ₃ ] (6–9) were inactive in ROP of L‐lactide. In addition, all of these Zn complexes demonstrated moderate activity in the reaction of CO₂ with cyclohexene oxide in the presence of Bu₄NCl.     

Biologically inspired 3Fe4S cluster as structural mimics of FeMoco M-cluster

A 3Fe4S cluster related to M-cluster of Mo-nitrogenase is reported. [K(THF)₅][Fe₃(μ-bdt)₂(μ-PPh₂)(CO)₅] ( 1 ) is synthesized from photo-assisted structural rearrangement of [K(THF)₂][(μ,κ²-bdt)Fe₂(μ-PPh₂)(CO)₅] under visible light irradiation. The molecular structure of 1 consists of a Fe₃ core bearing one dithiolate bridge and the second dithiolate group capping onto the metallic plane. The structural motif of 1 is analogous to that of Mo-participated 3Fe4S unit in M-cluster of Mo-nitrogenase, with the similar Fe-Fe and Fe-S bond distances. Upon protonation in 193 K, a Fe-hydride species ( 1H ) is generated and characterized to possess the bridging hydride group (δ = −12.57 ppm) by ¹H-NMR spectroscopy and DFT calculation. In CH₃CN solution, complex 1 exhibits a reversible reduction and oxidation process at $E_{1/2}^{\mathrm{red}}$ = −1.94 V and $E_{1/2}^{\mathrm{ox}}$ = −0.18 V, respectively, at 273 K. The reduction behavior of 1 in CH₂Cl₂ solution at 243 K displays a slight modification in the presence of trifluoroacetic acid, revealing a moderate anodic potential shift (~50 mV). The current amplitude of the reduction wave is linearly increased with the increasement of acid added, indicative of the catalytic event.     

环戊二烯类有机金属含硫族化学的新进展

本文系统地综述了环戊二烯类有机过渡金属含硫族(S, Se, Te) 化学领域的研究现状和进展。参考文献136 篇。     

化学学科的新视角及其在化学教育中的反映

传统化学以研究变化,关注变化前后的结果而著称。化学与其他学科,特别是生命科学的相互渗透使得化学的动态特征更加突出,化学学科格局也因之发生了变化。因此,化学需要新认识。     

Meeting the sustainable development goals in a tropical climate

This article reflects on the Federation of Asian Chemical Societies (FACS) Citation Award Lecture delivered in the Industrial Technology Research Institute Symposium on CO₂ Utilization and Green Technology during the 18th Asian Chemical Congress held in Taipei, December 12, 2019. Malaysia produces sizable amounts of palm oil and palm kernel oil, with palm fronds and tree trunks as the main waste. At the Malaysia Japan International Institute of Technology, the biomass was decomposed to produce fine chemicals, used as substrate for mushroom growth, and converted to bio-coke for heat energy. A notable difference has been found regarding the emission of greenhouse gases from a natural peat forest and those from the oil palm plantation converted from peatlands, where in the palm plantation, water table is lowered and aerobic processes occurs, resulting in more CO₂ being released compared to CH₄. The introduction of fertilizers to the plantation resulted in more N₂O being released. The team has also pioneered a project to plant temperate vegetables. Cooling pipes (16–18°C with circulating water cooled by chiller) were embedded within each thermal conditioning soil plot. Lettuce and radish, the experimental plants, showed good growth in the thermal conditioning soil due to nitrogen-fixing bacteria, which were destroyed at a higher temperature.