Fe/Co/N/MWCNTs催化剂的制备及性能

将掺杂铁离子的聚苯胺(PANI)与碳纳米管(MWCNT)复合物在900℃加热,得到含铁的催化剂FeNC;然后将含钴盐的FeNC在不同温度下焙烧,得到复合催化剂FeCoNC。对催化剂的表观结构、比表面积、热稳定性、组成以及氧还原(ORR)电催化活性进行表征,研究了焙烧温度和氮含量等因素对其催化活性的影响。结果表明:随着焙烧温度的升高,催化剂的表面结构趋于均匀,焙烧温度为500℃的催化剂表面结构最为均匀平整,高于500℃时出现烧结;较高的氮含量能改善催化剂的ORR电活性。焙烧温度为500℃的催化剂对ORR的电催化活性最高,在酸性和碱性溶液中ORR的起始电位分别为0.63和-0.12 V(vs SCE),电流密度分别为11.67和9.83 mAmg-1@-0.3 V(vs SCE),并具有较好的热稳定性和催化活性稳定性。分步加入Fe和Co,并在加Co后在500℃焙烧得到的催化剂对ORR具有优异的电催化活性。     

用于电催化氧还原制备双氧水的催化剂的研究进展

H2 O2及其水溶液双氧水具有强氧化性,被广泛应用于造纸、污水处理和消毒等方面.全球对H2 O2的需求量与日俱增,但传统的蒽醌法工艺复杂、成本高、效率低,氢氧直接合成法又存在很大的安全隐患.因此,电催化氧还原这种新型、绿色且安全的原位合成H2 O2方法近年来受到广泛关注.氧还原反应(ORR)是多电子反应,中间体复杂且难以测量,机理研究困难.ORR存在两种竞争的反应路径,两电子路径得到H2 O2,而四电子路径生成H2O.两电子氧还原反应(2e-ORR)的反应效率取决于催化剂的活性、选择性和稳定性.目前贵金属基催化剂(如Au、Pd)对2e-ORR显示出较好的催化性能,但昂贵、稀缺的特性限制了它们的广泛应用.当前关于电催化氧还原制备H2 O2所用催化剂的研究主要集中于三方面:(1)减少贵金属的负载.将惰性金属与活性金属相结合,得到了许多性能优异的合金材料,如Pt-Hg等.(2)发展非贵金属催化剂.碳基催化剂的缺陷、表面氧官能团(C=O、C-O等)、杂原子掺杂(N-、S-等)和过渡金属掺杂(Co、Fe等)都能够提高H2O2的选择性与催化活性.(3)发展非贵金属复合催化剂.非贵金属复合物催化剂(如MnO2/C、CoS2/C)可促进电子转移,提高H2 O2的选择性.本文系统介绍了2e-ORR的机理及测试方法,简要总结了近年来用于2e-ORR制H2 O2的贵金属基催化剂、碳基催化剂和非贵金属复合催化剂的研究进展,并在此基础上对电催化氧还原制双氧水未来的研究方向进行了展望.     

Co-MOF衍生Co-N-C催化剂的制备及其氧还原性能研究

金属-氮-碳(M-N-C)化合物作为非贵金属催化剂具有优异的氧还原(ORR)性能,在燃料电池和金属-空气电池等电化学能源转化方面展现了广阔的应用前景。开发出能够与贵金属铂催化剂相媲美的高效且廉价的催化剂以解决ORR缓慢动力学问题具有重要意义。选用金属有机骨架材料ZIF-67作为碳源和氮源,其中,二价钴离子、2-甲基咪唑和高分子聚合物聚乙烯亚胺(PEI)在室温下快速原位合成催化剂,PEI不仅能避免ZIF-67的团聚还提高了催化剂的氮含量。所制备出的纳米材料Co-N-C(ZIF-67+PEI)催化剂在碱性电解质中拥有优于商业Pt/C的ORR性能及稳定性和抗甲醇性能。     

石墨烯/金属氮杂环纳米复合材料在燃料电池分子氧催化还原反应中的应用研究

石墨烯具有良好的电子传导性、巨大的表面积、稳定的化学和机械稳定性等,在分子氧催化还原(ORR)反应中可以有效地改进催化剂的催化活性,是过渡金属大环催化剂新的基底材料。对石墨烯支持的非贵金属氮杂环复合材料在ORR催化反应中的应用以及影响催化O_2活性的因素进行了讨论。重点讨论了卟啉和酞菁中心金属核,Co和Fe,以及卟啉和酞菁作为N的前驱体对ORR电催化活性的影响,并展望了非贵金属氧还原催化剂在燃料电池中的研究发展方向。     

一步热解合成氮掺杂石墨烯载钴纳米粒子及其对氧还原反应的电催化性能

采用便捷的一步热解途径合成了氮掺杂石墨烯载钴纳米粒子(Co/NG),并表征了其结构、形貌和表面性质,进一步评价了Co/NG作为阴极催化剂对氧还原反应的电催化性能。透射电镜(TEM)和X射线粉末衍射(XRD)谱分析显示平均粒径21.4nm的Co纳米粒子较均匀地分散在三维多孔状石墨烯上。X射线光电子能谱(XPS)结果表明,Co/NG存在两类含氮组分,即吡啶氮和吡咯氮。电化学测试结果显示,Co/NG催化剂在碱性介质中对氧还原反应的起始还原电位约-0.049V,极限电流密度为5.9mA/cm~2。其电催化活性与商业化Pt/C相当。     

金属掺杂聚吡咯碳化物PPY-M的制备及其氧还原反应电催化活性

在Fe³⁺或Co²⁺存在下进行吡咯的聚合反应, 得到金属离子掺杂的聚吡咯, 并在N₂气氛下700℃碳化, 再将该碳化产物在900℃焙烧得到含有不同金属的复合催化剂PPY-M(M为不同的金属)。采用SEM、XRD等对催化剂的结构进行了表征。通过循环伏安和线性电位扫描等电化学手段, 研究了催化剂对氧还原(ORR)的电催化活性及其稳定性。结果表明, 掺杂金属钴的催化剂的活性最好, 在酸性溶液中ORR的起始电位达到0.54 V(vs SCE),电流密度为7.5 mA/mg@-0.3 V(vs SCE); 在碱性溶液中ORR的起始电位为-0.11 V(vs SCE),电流密度为5.7 mA/mg@-0.8 V。Fe或Co掺杂的聚吡咯碳化物对ORR具有较强的电催化活性, 而且制备过程简单、成本低, 有较重要的研究意义。     

钴氮共掺杂生物质活性炭提升氧化还原催化剂性能北大核心CSCD

采用新鲜海带为原料,先真空冷冻干燥,粉碎过筛后与一定量KOH干混,高温活化制备生物质活性炭,选取优化后的活性炭掺杂钴氮元素,经过高温煅烧形成Co-N-C型非贵重金属催化剂.结果表明,海带基生物质活性炭在活化温度为800℃,活化时间60 min下比表面积为2071. 72 m2/g,总孔容为1. 20 cm3/g,产率为25. 06%;该生物质活性炭掺杂钴氮元素获得的催化剂材料拥有很好的ORR(氧还原反应)活性、耐甲醇性和稳定性,可以被广泛的应用在能源领域.     

钴氮共掺杂生物质活性炭提升氧化还原催化剂性能

采用新鲜海带为原料,先真空冷冻干燥,粉碎过筛后与一定量KOH干混,高温活化制备生物质活性炭,选取优化后的活性炭掺杂钴氮元素,经过高温煅烧形成Co-N-C型非贵重金属催化剂.结果表明,海带基生物质活性炭在活化温度为800℃,活化时间60 min下比表面积为2071. 72 m2/g,总孔容为1. 20 cm3/g,产率为25. 06%;该生物质活性炭掺杂钴氮元素获得的催化剂材料拥有很好的ORR(氧还原反应)活性、耐甲醇性和稳定性,可以被广泛的应用在能源领域.     

Co修饰的碳载Pt纳米粒子催化剂的制备与表征

质子交换膜燃料电池阴极需要使用高活性的电催化剂来加速氧还原反应(ORR)速率,而提高活性成分贵金属铂(Pt)的功能反应利用率可解决其关键问题.本工作利用过渡金属钴Co(Ⅱ)?有机框架(Co?MOF)为前驱体合成ORR催化剂载体Co/C,并采取浸渍?液相还原法负载Pt纳米粒子制备了合金Pt?Co/C催化剂.通过对样品的孔隙结构、物相结构、微观形貌等表征,证实了载体Co/C具有较大的比表面积和相互连通的分级介孔结构,其独特的形貌、丰富的孔隙结构使负载的Pt纳米颗粒均匀分布、粒径范围窄,平均粒径约为6.8 nm.进一步对催化剂进行电化学性能评价,其电化学活性表面积(ECSA)接近于商用Pt/C催化剂的值,结果表明合金催化剂中活性成分Pt具有较高的利用率,同时还表现出载体独特的孔隙结构优势.     

过渡金属和磷共掺杂多孔碳作为氧气还原电催化剂

碳基材料作为非贵金属催化剂具有导电性能高、稳定性能好、价格低廉、环境友好等优点,在燃料电池阴极催化剂领域中引起了广泛的关注,尤其是过渡金属和异原子共掺杂能够显著提高碳材料的氧气还原催化活性。本文采用聚醚(F127)作为软模版,苯酚、甲醛作为碳源,四苯基溴化膦作为磷源,硝酸盐作为过渡金属来源,通过挥发溶剂自组装及高温煅烧过程制备了过渡金属(Co、Fe、Ni、Mn)和磷(P)共掺杂多孔碳材料(TM-P-C)。通过旋转环盘电极研究了TM-P-C在0.1 mol/L KOH电解液中的氧气还原电催化性能。研究结果表明：TM-P-C催化剂具有较高的氧化还原反应(ORR)电催化性能,其ORR活性为P-Co-C>P-NiC>P-Fe-C>P-Mn-C,其中P-Co-C的ORR电催化性能可与商业20wt%Pt/C催化剂相媲美,其电流密度与20wt%Pt/C催化剂的电流密度相当,与20wt%Pt/C仅存在66 mV的半波电位差,表现为ORR的4e–转移途径。制备的TM-P-C催化剂所具有的较高氧气还原电催化活性主要来自于过渡金属和P原子之间的协同作用。此外,TM-P-C催化剂表现出优异的...     

Structure of Trimethylbenzylammonium and Triethylbenzylammonium Tetrachlorouranilates

Radiochemistry - Synthesis, IR spectroscopic and X-ray structural studies of new chlorine-containing uranyl complexes (C10H16N)2[UO2Cl4] (I) and (C13H22N)2[UO2Cl4]0.5[UO2(NO3)2Cl2]0.5 (II) have...     

Effects of sodium modification, different reductants and SO(2) on NO reduction by Rh/Al(2)O(3) catalysts at excess O(2) conditions

Although many catalysts of NO reduction have been developed, the presence of excess O(2) and SO(2) significantly inhibits their performance when they are used to treat the incineration flue gas. To solve such problem, this study prepared new Rh/Al(2)O(3) catalysts and investigated the effects of Na modification, SO(2) and different reductants. Experimental results indicated that the average removal efficiency of NO at such high O(2) concentrations exceeded 80% when the Rh/Al(2)O(3) catalysts were used. CO was a better reductant than C(3)H(6) and the best concentration ratio of reductant/NO was equal to 1. Adding Na to modify Rh/Al(2)O(3) catalysts significantly enhanced the removal efficiency of NO from 80 to 99% at 250-300 degrees C, especially at relative high SO(2) concentrations. Unfortunately, Rh-Na/Al(2)O(3) catalysts do not have long-time activities for NO reduction, possibly because of the formation of NaNO(3). Both Rh/Al(2)O(3) and Rh-Na/Al(2)O(3) catalysts have good performance for NO reduction, they can feasibly be used to reduce NO in the flue gas from waste incineration.     

Effect of Sequence of Impregnation on the Structure and Catalytic Properties of Cu-Co-Al-Oxide System

Twelve samples of Co-Cu/AI2O3 were prepared by impregnating AI2O3 with cobalt salt followed by copper salt or vice versa. The composition of the prepared samples varied in the molar ratios 1:1, 1:2 and 1:3 with respect to CuO.CoO or CoO:CuO, while Al2O3 content was kept at about 13-15 mol. The prepared solids were calcined at different temperatures and the products were characterized by means of XRD-analysis. The catalytic activity of the calcined solids was tested in H2O2 decomposition. The XRD-analysis revealed that the sequence of impregnation affects much the structure of the samples. The loading of alumina with cobalt followed by copper salts produced sample with structure differs from that for sample firstly treated with copper followed by cobalt salts. XRD- analysis showed the formation of crystalline spinel Co1-x Cux AI2O4 with nearly the same crystal structure as CoAI2O4 even with high copper content. The examination of catalytic activity of these samples showed that catalysts with Co-loaded ov     

A study on N2O catalytic decomposition over Co/MgO catalysts

Different oxide supported cobalt catalysts were prepared by co-precipitation method and tested for the decomposition of nitrous oxide. Co/MgO with cobalt loading of 15% showed the best activity and a 100% N(2)O conversion was obtained at temperatures higher than 700 K. The active phase of cobalt species in Co/MgO catalysts was Co(3)O(4) highly dispersed in the matrices of MgO, based on XRD and XPS results as well as the kinetic analysis. The existence of NO, O(2) and H(2)O in reaction system showed different negative effects on N(2)O decomposition. Nevertheless, a 100% N(2)O conversion could be achieved at 800 K under simulated conditions of tail gas from nitric acid plant. Moreover, Co/MgO catalyst exhibited quite good durability and no obvious activity loss was observed in the 100 h stability test.     

Use of EAF dust as heterogeneous catalyst in Fenton oxidation of PCP contaminated wastewaters

In this study, chemical oxidation tests using H2O2 were performed on a solution contaminated with 100 mg l(-1) of pentachlorophenol (PCP). The effectiveness of electric arc furnace dust and hematite as heterogeneous catalysts was evaluated. Reactions were conducted at pH 2 for 24 h. Either H2O2 stabilized with KH2PO4 or un-stabilized H2O2 was used. Total organic carbon (T.O.C.) removal and chloride release from PCP molecule were monitored. Results showed that the maximum removal yields for electric arc furnace (EAF) dust (49.2% T.O.C., 56.7% Cl) were achieved when H2O2:PCP ratio was 10:1 and Fe:H2O2 = 1:5 for unstabilized H2O2 and when H2O2:PCP = 10:1 and Fe:H2O2 = 1:1 for stabilized H2O2 (48% T.O.C., 60.6% Cl). The maximum yield using hematite (45.2% T.O.C., 55.2% Cl) was obtained when H2O2:PCP ratio was 10:1 and Fe:H2O2 was 1:2. When EAF dust was used and Fe:H2O2 > 1:5, Cl release was higher than the one expected from T.O.C. removal.     

Synthesis and Structure of Uranyl Succinate Complex with Isonicotinic Acid and New Polymorph of Uranyl Succinate Monohydrate

Radiochemistry - Synthesis, IR spectroscopic and X-ray structural studies of crystals [UO2(C4H4O4)(C6H5NO2)2] (I) and a new modification [UO2(C4H4O4)(H2O)] (II), where C4H4O42– are succinate...     

钯钌原子比对碳载Pd-Ru催化剂催化H2O2电还原性能影响

利用化学还原法制备了不同原子比的碳载Pd-Ru催化剂,考察了钯钌原子比对碳载Pd-Ru催化剂催化H2O2电还原反应性能的影响。研究结果表明,随着Ru元素的增加,碳载Pd-Ru催化剂的粒径逐渐减小,各催化剂上H2O2电还原反应的起始还原电势稳定在0.82V,电流密度先增大后减小。当Pd∶Ru=1∶1时,PdRu/C催化剂表现了最好的催化性能。     

原位合成La_2Zr_2O_7-YSZ复合材料及高温热稳定性研究

以硝酸锆、硝酸镧、硝酸钇和柠檬酸为原料,原位合成了La2Zr2O7、氧化钇稳定氧化锆(YSZ)及其La2Zr2O7-YSZ复合材料。采用X射线衍射和拉曼光谱对样品进行分析和表征,研究La2Zr2O7、YSZ和La2Zr2O7-YSZ复合材料的物相组成与高温热稳定性。结果表明:合成的La2Zr2O7和YSZ均为单一纯相。在1 200℃煅烧6 h条件下合成的系列复合材料(物质的量比n(La2Zr2O7)∶n(YSZ)=1∶8~10∶1)中均未发现单斜ZrO2相和其他化合物的生成。在1 400℃煅烧24 h条件下合成的LZYZ11中出现单斜ZrO2相,此时La2Zr2O7对YSZ的稳定效果不大。     

Application of mixed oxide catalysts to the removal of lean NOx and N2O using transient-mode cyclic operations

The storage and reduction of NO and N2O in the presence of excess O2 have been investigated over two mixed oxide catalysts. The catalysts, which were prepared via coprecipitation of solutions of mixed metal nitrates, followed by calcination, were found to have plenty storage capacities for nitrogen oxides. The storage and reduction performances varied with the catalyst composition and the duration of cycle time: the AlCoPd (1/1/0.05) mixed oxide catalyst exhibited higher efficiency for NO, and an AlCoFe (1/1/2) mixed oxide catalyst exhibited higher efficiency for N2O. The adsorptions of NO and N2O onto the mixed oxide catalysts progressed without an oxidation step, and the adsorptivity of NO surpassed that of O2. The mixed oxides showed spinel structures with sizes of 10-100 nm, and with well-developed mesopores that were formed by the evaporation of H2O and CO2 from layered double hydroxide (LDH) precursors. The storage and reduction of lean NOx and N2O over the mixed oxide catalysts were carried out via cyclic operations in a transient mode at 300 degrees C and at space velocities of around 30,000 h(-1). The removal efficiency of the cyclic operations generally increased with reduced adsorption cycle time, and reached 90% for NOx and N2O with the respective catalysts.     

Vibrational spectroscopic studies and density functional theory calculations of speciation in the CO2-water system

Raman spectra of CO(2) dissolved in water and heavy water were measured at 22 degrees C, and the Fermi doublet of CO(2), normally at 1285.45 and 1388.15 cm(-1) in the gaseous state, revealed differences in normal water and heavy water, although no symmetry lowering of the hydrated CO(2) could be detected. Raman spectra of crystalline KHCO(3) and KDCO(3) were measured at 22 degrees C and compared with the infrared data from the literature. In these solids, (H(D)CO(3))(2)(2-) dimers exist and the spectra reveal strong intramolecular coupling. The vibrational data of the dimer (C(2h) symmetry) were compared with the values from density functional theory (DFT) calculations and the agreement is fair. Careful measurements were made of the Raman spectra of aqueous KHCO(3), and KDCO(3) solutions in D(2)O down to 50 cm(-1) and, in some cases, down to very low concentrations (> or =0.0026 mol/kg). In order to complement the spectroscopic assignments, infrared solution spectra were also measured. The vibrational spectra of HCO(3)(-)(aq) and DCO(3)(-)(D(2)O) were assigned, and the measured data compared well with data derived from DFT calculations. The symmetry for HCO(3)(-)(aq) is C(1), while the gas-phase structure of HCO(3)(-) possesses Cs symmetry. No dimers could be found in aqueous solutions, but at the highest KHCO(3) concentration (3.270 mol/kg) intermolecular coupling between HCO(3)(-)(aq) anions could be detected. KHCO(3) solutions do not dissolve congruently, and with increasing concentrations of the salt increasing amounts of carbonate could be detected. Raman and infrared spectra of aqueous Na(2) -, K(2) -, and Cs(2)CO(3) solutions in water and heavy water were measured down to 50 cm(-1) and in some cases down to extremely low concentrations (0.002 mol/kg) and up to the saturation state. For carbonate in aqueous solution a symmetry breaking of the D(3h) symmetry could be detected similar to the situation in aqueous nitrate solutions. Strong hydration of carbonate in aqueous solution could be detected by Raman spectroscopy. The hydrogen bonds between carbonate in heavy water are stronger than the ones in normal water. In sodium and potassium carbonate solutions no contact ion pairs could be detected even up to the saturated solutions. However, solvent separated ion pairs were inferred in concentrated solutions in accordance with recent dielectric relaxation spectroscopy (DRS) measurements. Quantitative Raman measurements of the hydrolysis of carbonate in aqueous K(2)CO(3) solutions were carried out and the hydrolysis degree a was determined as a function of concentration at 22 degrees C. The second dissociation constant, pK(2), of the carbonic acid was determined to be equal to 10.38 at 22 degrees C.