Au/CeO2催化剂上CO2选择加氢为CO反应及其中间物种研究

CO2的化学转化具有环境及科学双重研究意义.CO2具有很高的化学稳定性,加氢还原是一种有效的转化途径.其中将CO2选择性还原为CO,即逆水汽变换(RWGS)反应(CO2+H2→CO+H2O),具有重要的理论意义和应用价值:(1)CO作为合成气的重要原料,可以通过F-T合成生产更有价值的液体燃料;(2)H2可通过可再生能源电解水制取,实现了全过程的零排放碳循环利用.从热力学角度分析,RWGS反应是一个吸热反应,高温有利于平衡转化率的提高.从动力学角度,一个对正反应有活性的催化剂可同时催化逆反应进行.可还原性载体负载贵金属催化剂,如Pt/CeO2,Au/FeOx,Au/CeO2等,具有很好的低温WGS催化活性,但它们在RWGS反应上的研究较少.我们制备了CeO2负载纳米Au催化剂(HRTEM表征结果表明金高度分散于CeO2载体表面,粒径为4-5 nm),其在常压CO2加氢还原为CO反应中表现出优异的低温活性,分别在450℃,CO2/H2=1,WHSV=12000 mL/(h·g),及400℃,H2/CO2=1,WHSV=6000 mL/(h·g)条件下,CO2转化率接近平衡转化率,且CO的选择性为100%.随着H2/CO2比例增加,CO2转化率明显提高,且维持H2/CO2为1的化学计量比反应.通过原位漫反射红外光谱与质谱相结合的技术,研究了Au/CeO2催化剂上的RWGS反应路径:Au/CeO2催化剂表面形成了甲酸盐中间物种,它的消耗伴随着CO和H2O产物的生成.说明Au/CeO2催化剂遵循中间体机理,这应该是其具有优异低温RWGS反应性能的微观机制.     

二氧化钛基Z型光催化剂综述(英文)

TiO_2具有无毒、耐腐蚀、高稳定和低成本等特点,已被广泛应用于光催化领域.然而,TiO_2的禁带较宽,只能吸收仅占太阳光4%的紫外光部分,从而严重限制了TiO_2光催化材料对太阳光的有效应用.目前很多方法被用来提高TiO_2光催化效率,如金属/非金属掺杂、贵金属负载、异质结构建和与碳材料复合等,这些策略在提高光催化剂的光催化效率中,涉及到如何兼顾太阳光利用和光生空穴和电子氧化还原能力两者之间的平衡.通常,半导体禁带宽度越窄,半导体的光谱响应范围越宽、太阳光利用越多,但光生空穴和电子氧化还原能力越弱.因此,想要提高TiO_2的光催化性能,应考虑以下两个方面的平衡:即降低带隙宽度,拓展半导体的光谱响应范围;与之同时使价带电位更正,导带电位更负之间的平衡.然而,这两个点是相互矛盾的,因此很难在单组分光催化剂中同时实现这两点.然而,Z型光催化剂可以同时满足这两点要求,即:降低半导体的带隙,同时使导带更负,价带更正,因为Z光催化系统利用了两种半导体的优势,其电荷转移机制类似于自然界中绿色植物的光合作用,其中的载流子传输途径包括两步激发,类似于英文字母"Z",Z型光催化剂因此而得名.Z型光催化剂既能保留较高还原能力的光生电子和又能保留较高氧化能力的光生空穴,由于Z型光催化剂特有的优点,在光催化领域的应用越来越广泛.本文综述了TiO_2基Z型光催化剂的最新研究进展,其中包括:Z型光催化机理、应用范围和光催化活性改进方法.Z型光催化剂分为传统液相Z型光催化体系,全固态Z型光催化体系,以及最近几年发展起来的直接Z型光催化体系.它们的主要应用包括:光催化分解水产氢、二氧化碳还原制备太阳燃料、有机污染物光催化降解.论文进一步讨论了提高TiO_2基Z型光催化剂性能的方法,包括pH值调控、电子导体选择、助催化剂使用、掺杂改性、组织形貌控制、两种半导体质量比优化等.最后,提出了TiO_2基Z型光催化剂今后面临的挑战和发展前景展望.     

金属纳米簇在CO2光催化还原中的研究进展

化石燃料的大量燃烧不仅造成能源危机,而且排放的二氧化碳（CO2）会使气候变暖。以清洁、储量丰富的太阳光作为能量来源,将CO2光催化还原为高附加值的化学产品是缓解当前环境问题和能源问题的主要方法之一。然而,CO2在常温常压下非常的稳定,因此需要设计并构筑高效光催化剂来捕捉和转化CO2,以达到高效光催化CO2还原的目的。在众多研究的光催化剂中,金属纳米簇因其具有独特的结构特点、优异的物理和化学性质,所以在光催化CO2还原领域得到了广泛的应用。基于此,我们首先对金属纳米簇进行了分类,将其分为贵金属纳米簇和非贵金属纳米簇;然后分别对贵金属和非贵金属纳米簇在光催化CO2还原中的研究进展进行了归纳与总结。本文通过及时全面概述近几年该领域的研究进展,从而为未来研究方向提供新思路。     

Photodecomposition of water with methane over titanium oxide photocatalysts modified with metal

Metal-loaded titanium oxide photocatalysts produced hydrogen in the photodecomposition of water vapor with methane in the flow reactor. Ag/TiO₂ has the highest activity in comparison with other metal-loaded catalysts. The experiment in the absence of methane indicated that methane could effectively function as a reducing reagent of water. The significant decrease in the hydrogen formation rate with the time on stream was observed under all reaction conditions. The recalcination and the hydrogen rereduction of the used catalyst led to the restoration of the activity of the hydrogen formation. The adsorption of products and/or reactants on the catalyst surface seemed to cause these deactivations of the hydrogen formation.     

溶胶-凝胶法制备Cr-基催化剂及其CO2氧化乙烷制乙烯

以硝酸铬为Cr源,正硅酸乙酯为Si源,采用溶胶-凝胶法制备了Cr质量分数为2.5%~10%的Cr-基催化剂;采用XRD、BET、SEM、H₂ TPR等分析测试技术对催化剂的结构进行了表征;在微型固定床反应器中对催化剂乙烷二氧化碳氧化脱氢制乙烯的催化性能进行了评价,并考察了反应条件对催化性能的影响。结果表明,催化剂中Cr的质量分数大于5%时,Cr的物相为Cr₂O₃,但Cr质量分数较低时,检测不到Cr的物相;Cr质量分数为5%的催化剂具有较大的比表面积,Cr质量分数变大或变小,催化剂的比表面积都会减小;催化剂的孔径在2nm左右,并与Cr的质量分数关系不大;Cr质量分数为5%的催化剂具有最好的催化活性,在750℃的反应条件下,乙烷和二氧化碳的转化率可达79.29%和23.74%,乙烯的收率可达67.91%;Cr质量分数为5%的催化剂具有适宜的氧化还原性能,这有利于乙烷和二氧化碳的转化。     

Sorption of carbon dioxide in fluorinated poyimides

Sorption isotherms of CO₂ for ten fluorinated polyimides measured at 35°C and up to about 25 atm are analyzed according to the dual-mode sorption model. Sorption properties for these polyimides are compared with those for other glassy Polymers including unfluorinated polyimides. The glassy polymers with higher glass transition temperatures T_g tend to show greater CO₂ sorption. Introduction of a ? C (CF₃)₂? linkage into the repeat unit of the main chain increases the sorption by 20–80%. For glassy polymers, including the fluorinated and unfluorinated polyimides, the Langmuir affinity constant b and Henry's law solubility constant k_D are correlated with the content of functional (carbonyl or sulfonyl) groups [FG], and composite parameter reflecting the magnitude of both [FG] and free-space fraction V_F, respectively, with some exceptions. The Langmuir capacity constant C′_H is correlated with T_g, but there are two correlation lines; one for unfluorinated polyimides and a different one for other glassy polymers including fluorinated polyimides. The slope of the former group is smaller probably because of smaller differences in thermal probably because of smaller differences in thermal expansion coefficients in rubbery and glassy states. Most fluorinated polyimides show greater solubility of CO₂ than unfluorinated polyimides and other glassy polymers, because of their larger C′_H and k_D. © 1993 John Wiley & Sons, Inc.     

水蒸气对甲烷在金属铁表面还原NO行为的影响

采用程序控温电加热水平陶瓷管反应器,在N2气氛和模拟烟气气氛中、300~1100℃下,研究了水蒸气对甲烷在金属铁表面还原NO行为的影响,并对反应前、后铁样品进行了X光衍射(XRD)、扫描电子显微镜(SEM)及X光电子能谱(XPS)等表征。结果表明,水蒸气对甲烷在金属铁表面还原NO行为的影响较小。在N2气氛中,水蒸气参与了金属铁的氧化;与无水蒸气时相比,水蒸气存在时NO还原效率有所下降。当水蒸气含量从2.5%增加到7%时,由于水蒸气对金属铁的氧化导致其表面形成疏松的微观孔隙,使得NO的还原效率随水蒸气含量的增加而提高。甲烷则参与了铁氧化物的还原,使铁样品表面形成相对致密的Fe3O4和FeO氧化层,不利于NO与金属铁的接触,使得NO的还原效率低于无甲烷时的结果。在模拟烟气条件下,水蒸气使得甲烷在金属铁表面还原NO的效率增加;在1050℃下,反应段过量空气系数SR1=0.7和燃尽段过量空气系数SR2=1.2时,含7%的H2O和无H2O条件下脱硝效率分别为96.7%和90.6%。而在湿烟气中SO2使NO还原效率略有下降。持久性脱硝实验结果表明,当反应温度为1050℃时,在含7%的H2O、0.02%的SO2的模拟烟气中,1.14%的甲烷在金属铁表面持续50h都能保持90%以上的脱硝效率。     

Selective visible light reduction of carbon dioxide over iridium(III)-terpyridine photocatalysts

The CO₂ reduction reaction is an imperative piece of technology that closes the carbon cycle in many critical energy conversion and chemical manufacturing processes. Here, we report two new iridium (III) terpyridine-based photocatalysts capable of selective reduction of CO₂ to CO under visible light (λ ≥ 420 nm). The first photocatalyst, [Ir–COOH], was functionalized with the carboxyl group on the phenylpyridine, whereas the second, [Ir-PhCOOH], was attached to a phenyl spacer on the terpyridine. The [Ir-PhCOOH] was characterized by a higher extinction coefficient than [Ir–COOH], thus allowing more absorption of photons. Although both photocatalysts require two-electron activation, the [Ir-PhCOOH] is more readily activated as a result of the more negatively charged Ir center. These photocatalysts show exclusive selectivities in the production of CO. The turnover frequencies for [Ir–COOH] and [Ir-PhCOOH] were 19 and 10 h^?1, respectively, under visible light irradiation. The e-e-H-H pathway was identified as the most favorable, consisting of the rate-limiting step in the conversion of 1COOH to 1CO, and where the barrier is significantly lower for [Ir-PhCOOH] than for [Ir–COOH].     

Deoxygenative reduction of carbon dioxide to methane, toluene, and diphenylmethane with [Et2Al]+ as catalyst

The strong Lewis acid [Et(2)Al](+) catalyzes the reduction of carbon dioxide with hydrosilanes under mild conditions to methane. In benzene solution, the side products toluene and diphenylmethane are also obtained through Lewis acid catalyzed benzene alkylation by reaction intermediates.     

氩气回路中甲烷和二氧化碳杂质的分析方法研究

本文1：1地模拟了正在建造的中国实验快中子反应堆的气体回路，建立了一个工程上可行的、50m长的、有多条固定管线和阀门的快堆覆盖气体放射性氩气取样系统、计算机控制的阀门进样以及氩气中杂质CH4和CO2的间断性在线分析方法。通过热导检测器出口气体可以排放入通风系统的办法，避免了使用氢火焰离子化检测器以后，放射性气体氩气扩散排放到气体分析实验室产生工作环境的放射性污染问题。其检出限、测量精度和准确度满足了中国实验快堆规定的氩气中杂质CH4和CO2的分析要求。并达到了美国试验和材料协会（ASTM）在快堆覆盖气体杂质的标准中提出的分析氩气中杂质CH4和CO2的标准。     

The production of carbon nanotubes from carbon dioxide: challenges and opportunities

Recent advances in the production of carbon nanotubes (CNTs) are reviewed with an emphasis on the use of carbon dioxide (CO2) as a sole source of carbon. Compared to the most widely used carbon precursors such as graphite, methane, acetylene, ethanol, ethylene, and coal-derived hydrocarbons, CO2 is competitively cheaper with relatively high carbon yield content. However, CNT synthesis from CO2 is a newly emerging technology, and hence it needs to be explored further. A theoretical and analytical comparison of the currently existing CNT-CO2 synthesis techniques is given including a review of some of the process parameters (i.e., temperature, pressure, catalyst, etc.) that affect the CO2 reduction rate. Such analysis indicates that there is still a fundamental need to further explore the following aspects so as to realize the full potential of CO2 based CNT technology: (1) the CNT-CO2 synthesis and formation mechanism, (2) catalytic effects of transitional metals and mechanisms, (3) utilization of metallocenes in the CNT-CO2 reactions, (4) applicability of ferrite-organometallic compounds in the CNT-CO2 synthesis reactions, and (5) the effects of process parameters such as temperature, etc.     

In situ FT-IR study on CO2 hydrogenation over SiO2-supported PtM (M = Cr, Mo, W) complex catalysts

The in situ FT-IR spectra were used to study the CO₂ hydrogenation reaction over the SiO₂-supported heterobinuclear metal complex catalysts, PtM (M=Cr, Mo, W). The bands, which correspond to the formate species absorbed on the catalysts, were observed. During the hydrogenation reactions, the adsorbed linear and bridging CO was not observed. The experimental results suggest that for the CO₂ and CO hydrogenation reaction over the same catalysts, their catalytic active intermediate species and the reaction mechanisms should be different.     

NO reduction and CO oxidation over Cu/Ce/Mg/Al mixed oxide catalyst in FCC operation

Simultaneous NO reduction and CO oxidation in the presence of O₂, H₂O and SO₂ over Cu/Mg/Al/O (Cu-cat), Ce/Mg/Al/O (Ce-cat) and Cu/Ce/Mg/Al/O (CuCe-cat) were studied. At low temperatures (<340 °C), the presence of O₂ or H₂O enhanced the activity of CuCe-cat for NO and CO conversions, but significantly suppressed the activity of Cu-cat and Ce-cat. At high temperature (720 °C), the presence of O₂ or H₂O had no adverse effect on the NO and CO conversions over these catalysts. The addition of SO₂ to NO+CO+O₂+H₂O system had no effect on the reaction of CO+O₂ over Cu-cat, but deactivated this catalyst for NO+CO and CO+H₂O reactions; over Ce-cat, all of these reactions of NO+CO,CO+O₂ and CO+H₂O were suppressed significantly; over CuCe-cat, NO+CO and CO+O₂ reactions were not affected while the reaction of CO+H₂O was slightly inhibited.     

"反应环境磷酸化"加速g-C3N4/碳纸气-液-固三相界面光催化CO2还原

采用悬浮体系进行光催化CO2还原反应是将半导体光催化剂均匀分散到液相中,但液相中有限的CO2溶解度和扩散速率,极大限制了光催化还原CO2反应的活性和选择性.为了提高悬浮体系的CO2还原活性,研究人员进行了一系列研究,包括开发新材料、形貌调控、复合光催化剂和用CO2饱和溶液代替纯水等.但这些改进策略对CO2还原活性的提升是有限的,仍然难以达到实际应用的要求.近年来,关于催化剂的设计和制备方面取得较大进步,但仅有极少数的研究致力于构建有效的光催化体系.实际上,光催化体系的构建与催化剂的设计和制备同样重要,因为理想的光催化CO2还原体系会使CO2反应气体与光催化剂的相互作用最大化,从而提高CO2还原反应的效率.近年来,可以建立气-液-固三相接触界面的疏水基底材料被广泛研究并应用于许多领域,包括燃料电池、光催化、电催化和有机合成等.这种独特的界面体系可以使反应气体到达反应界面并吸附在催化剂表面,从而提高了许多涉及气体的多相反应的反应速率.在传统的固-液两相体系中,气体传输通常是限制反应速率的因素,疏水基底的引入则可以很好地解决这一问题.氮化碳(g-C3N4)作为一种聚合物半导体,具有可见光响应能力,并且光生电子具有足够的还原能力满足还原CO2的需求,这使得它逐渐成为光催化CO2还原领域的明星材料.本文把g-C3N4作为光催化剂负载到疏水基底表面,构建气-液-固三相光催化体系并用于研究光催化CO2还原反应活性.以三聚氰胺为前驱体,采用化学气相沉积法在亲、疏水碳纤维纸表面生长g-C3N4光催化剂来构建新型气-液-固三相光催化体系,该体系可以增强CO2的传输和吸附能力,并形成气-液-固(CO2-H2O-光催化剂)三相反应界面,使得光催化CO2还原反应的活性和选择性显著提高.借助于疏水表面,气态物质可以连续不断地输送到光催化剂表面,而不仅依赖于溶解在液相中的微量CO2气体.因此,催化剂表面可以保持有较高的CO2和较低的H+浓度,在抑制析氢反应的同时增强CO2还原反应.研究结果表明,与亲水样品相比,疏水样品的CO2还原效率显著提高并明显抑制了析氢反应,其光催化CO2还原反应的选择性达到78.6％.另外,氧化半反应通常是光催化CO2还原反应的限制因素,会导致光生空穴的大量聚集,阻碍光生载流子的分离与传递,进而影响整体的光催化转化率.研究结果表明,使用磷酸盐溶液代替纯水进行光催化CO2还原反应性能,可以大幅提高气-液-固三相体系的光催化活性,其总体光催化CO2还原速率达到了1175.5 μmol h-1 m-2,是纯水环境下的8.8倍,CO2还原选择性为93.8％.光催化剂表面的光生空穴可以直接与溶液中的磷酸根离子发生反应,使磷酸盐反应生成过磷酸盐,以代替较难发生的产氧半反应.     

Electrochemical approach to evaluate the mechanism of photocatalytic water splitting on oxide photocatalysts

Photoelectrochemical measurements of TiO₂, NaTaO₃, and Cr or Sb doped TiO₂ and SrTiO₃ photocatalysts were carried out in H₂ and O₂ saturated electrolytes in order to evaluate the reverse reactions during water photolysis. The poor activity of TiO₂ as a result of reverse photoreactions of O₂ reduction and H₂ oxidation was revealed with the respective high cathodic and anodic photocurrents. The rise in the photocurrents at NaTaO₃ after La doping was in harmony with the doping-induced increase in the photocatalytic activity. NiO loading suppresses the O₂ photoreverse reactions, which declines photocatalytic activity, and/or promotes the photo-oxidation of water, because the O₂ photo-reduction current was scarcely observed near the flatband potential. Photocurrents of O₂ reduction and H₂ oxidation were observed under visible light for the Cr and Sb doped SrTiO₃ and TiO₂, respectively. These phenomena are in harmony with the previous reports on the photocatalysts examined with sacrificial reagents.     

反应气中活化后的镍酸镧用于二氧化碳加氢生成甲烷

采用柠檬酸法制备了钙钛矿镍酸镧,并将其作为催化剂的前躯体用于二氧化碳甲烷化反应中。催化剂在400℃~700℃温度下反应气中进行活化处理。活化过程中生成了金属镍颗粒和碳酸氧化镧。金属镍呈高度分散状并被碳酸氧化镧包裹,这种现象有助于反应在400℃和500℃的高温下仍保持高活性和稳定性。XRD、XPS、TEM和H₂-TPD等表征测试表明,在活化过程中生成的碳酸氧化镧对反应起到了至关重要的作用。     

二氧化硫脲对有机化合物的还原作用研究

报道了在碱性醇水溶液中，二氧化硫脲对含有硝基、羰基及烯键的有机化合物的还原作用，研究了这些反应的反应条件、反应产物和反应机理。     

The facile reduction of carbon dioxide to carbon monoxide with an amido-digermyne

Taking the fizz out: A digermyne compound with a Ge?Ge single bond has been shown to quantitatively reduce CO(2) to CO at temperatures as low as -40?°C. The mechanism of this unprecedented reaction has been probed by spectroscopic and computational techniques and involves a metastable intermediate (see picture; Ar*=C(6) H(2) {C(H)Ph(2) }(2) Me-2,6,4).     

多金属氧酸盐材料在二氧化碳电催化还原领域中的研究进展

随着工业发展和全球人口的持续增长,人类对化石燃料的消耗日益增加,从而导致大气中二氧化碳含量的显著增加以及与之相伴的一系列环境问题.电化学还原二氧化碳制备高附加值的燃料和化学品具有稳定的效率和较高的经济可行性等特点,目前已成为一种有前景的策略来缓解当前全球面临的能源短缺和气候变暖问题.然而,电催化二氧化碳还原过程存在反应...