Synthesis,crystal structure and photo-physical properties of tris(4-methyl-2,5-diphenylpyridine)iridium for OLED

Organic light-emitting diodes(OLEDs)have important applications in the field of next-generation displays and lighting,and phosphorescent iridium complexes are an important class of electroluminescent phosphorescent materials.In this paper,Ir(bmppy)_(3),tris(4-methyl-2,5-diphenylpyridine)iridium,was synthesized and elvaluted for photo-physical characteristics.Single crystals suitale for X-ray diffraction(XRD)were grown from a mixture solvent of dichloromethane and absolute ethanol.The composition and structur of Ir(bmppy)_(3)were determined by element analysis,NMR spectra and XRD.The complex crystallizes in the monoclinic symmetry with the space group P21/c with a slightly distorted octahedral configuration.As measured by UV-Visible and photoluminescence spectra,Ir(bmppy)_(3) displays a maximum emission at at 527 nm at ambient temperature,a typical green-emitting profile.The complex has potential for application in the OLED industry.

Gold-iridium bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

Carbon supported gold-iridium composite(Au Ir/C) was synthesized by a facile one-step process and was investigated as the bifunctional catalyst for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The physical properties of the Au Ir/C composite were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). Although the Au and Ir in the Au Ir/C did not form alloy, it is clear that the introduction of Ir decreases the average Au particle size to 4.2 nm compared to that in the Au/C(10.1 nm). By systematical analysis on chemical state of metal surface via XPS and the electrochemical results, it was found that the Au surface for the Au/C can be activated by potential cycling from 0.12 V to 1.72 V, resulting in the increased surface roughness of Au,thus improving the ORR activity. By the same potential cycling, the Ir surface of the Ir/C was irreversibly oxidized, leading to degraded ORR activity but uninfluenced OER activity. For the Au Ir/C, Ir protects Au against being oxidized due to the lower electronegativity of Ir. Combining the advantages of Au and Ir in catalyzing ORR and OER, the Au Ir/C catalyst displays an enhanced catalytic activity to the ORR and a comparable OER activity. In the 50-cycle accelerated aging test for the ORR and OER, the Au Ir/C displayed a satisfied stability, suggesting that the Au Ir/C catalyst is a potential bifunctional catalyst for the oxygen electrode.

高性能Ir基阳极双催化层阴离子交换膜电解水

设计高性能低Ir阳极催化层对阴离子交换膜电解水(AEMWE)商业化发展至关重要。本研究采用催化剂涂覆基底(CCS)方法,构建基于氧化铱(IrO_(2))和碳载铱(IrC)双催化层的阳极结构,提出了一种新型双Ir催化层并提高了AEMWE性能。研究表明,在IrC-IrO_(2)(先喷涂碳载铱,后喷涂氧化铱)催化层中,IrC高度分散特性有利于提高催化层中Ir的利用率,优化了催化层内电子、氢氧根离子的传输。采用商业Pt/C催化剂作为阴极,IrC-IrO_(2)阳极双催化层组装成碱性膜电极,在1 mol/L KOH电解质条件下,2.0 V时IrC-IrO_(2)电极达到了2.31 A/cm^(2)的高电流密度,而且在低浓度电解质以及纯水中依旧保持较高的性能。本研究为碱性膜电解水技术高效催化层的设计提供了参考。

Comparative characterization of iridium loading on catalyst assessment under different conditions

To discuss the potential role of iridium(Ir)nanoparticles loaded under atmospheric and high pressures,we prepared a series of cata-lysts with the same active phase but different contents of 10wt%,20wt%,and 30wt%on gamma-alumina for decomposition of hydrazine.Un-der atmospheric pressure,the performance of the catalyst was better when 30wt%of the Ir nanoparticles was used with chelating agent that had greater selectivity of approximately 27%.The increase in the reaction rate from 175 to 220 h^(−1)at higher Ir loading(30wt%)was due to a good dispersion of high-number active phases rather than an agglomeration surface.As a satisfactory result of this investigation at high pressure,Ir catalysts with different weight percentages showed the same stability against crushing and activity with a characteristic velocity of approxim-ately 1300 m/s.

MnO_(2)-0.39IrO_(x)复合氧化物用于酸性介质中水氧化反应的性能

通过Adams方法成功制备MnO_(2)-0.39IrO_(x)(0.39为Ir/Mn的原子比)催化剂并将其用于酸性介质中高效析氧反应(OER)。电化学测试发现,MnO_(2)-0.39IrO_(x)仅需253 mV的过电势即可驱动10 mA·cm^(-2)的水氧化电流密度,并可稳定运行200 h。在1.50 V(vs RHE)电势下,MnO_(2)-0.39IrO_(x)的贵金属Ir的质量活性为61.3 mA·mg^(-1),是IrO2的35.8倍,说明MnO_(2)掺杂大大提升了贵金属利用率。结构分析发现MnO_(2)-0.39IrO_(x)独特的片状结构大幅度提高了催化剂的电化学活性表面积,并且Ir位点与Mn位点之间存在一定的电子相互作用。催化过程分析表明,MnO_(2)-0.39IrO_(x)表面出现一定的重构现象,并且Mn组分对Ir位点的化学环境实现了持续优化,从而实现了催化剂的高效酸性OER性能。

Characterization of termetallic Pt-Ir-Au catalysts for NO decomposition

A termetallic catalyst of Pt-Ir-Au/Al2O3 for NOx decomposition was prepared by loading the metallic colloids in C2H5OH-H2O solution and a surfactant of polyvinyl pyrrolidone.Compared with an impregnated Pt/Al2O3 catalyst,the termetallic catalyst of PtIrAu811/Al2O3,with a Pt：Ir：Au atomic ratio of 8：1：1,exhibited higher NO decomposition and selectivity to N2.Transmission electron microscopy and X-ray diffraction were conducted to clarify the state of the supported metals and indicate three precious metals alloyed on the catalyst.In the study of NO-temperature programmed desorption,oxygen desorption on the PtIrAu811 catalyst shifted to the low temperature side compared to that on Pt/Al2O3,which correlated well with its higher catalytic performance in NO decomposition.

Superior performance of iridium supported on rutile titania for the catalytic decomposition of N_2O propellants

N2O is a promising green propellant and exhibits great potential for satellite propulsion systems. It is difficult for catalytic decomposition, which is an important way to initiate the propulsion process, to occur at temperatures below 600 °C due to the high activation energy of N2O. In this work, we report an Ir supported on rutile TiO2（Ir/r-TiO2） catalyst which exhibits a fairly high activity for high-concentration N2O decomposition. HAADF-STEM, H2-TPR, and XPS results indicate that highly dispersed Ir particles and improved oxygen mobility on the Ir/r-TiO2 could facilitate the decompo-sition of N2O and desorption of the adsorbed oxygen. Bridge-bonded peroxide intermediates were observed with in-situ DRIFT and herein, a detailed decomposition route is proposed.

Layered double hydroxide-like Mg_3Al_(1–x)Fe_x materials as supports for Ir catalysts: Promotional effects of Fe doping in selective hydrogenation of cinnamaldehyde

Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg3Al1-xFex,containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg3Al)to 1(Ir/Mg3Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg3Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg3Al1–xFex support to the dispersed Ir particles and the surface geometry.

负载Ir单原子和团簇的α-MoC催化剂用于高效催化CO_(2)加氢制CO

在高温逆水气变换(RWGS)反应中,开发高活性和高稳定性的金属负载型催化剂还存在巨大挑战。针对此问题,本研究采用溶液蒸发自组装法构建了Ir物种负载于α-Mo C的协同催化剂,结果表明,Ir与α-Mo C的协同效应使其在较宽的温度范围内均有较好的RWGS反应性能。特别是在500℃、0.1 MPa、300000 mL·g^(-1)·h^(-1)的反应条件下,0.5%Ir/MoC催化剂的CO_(2)转化率高达48.4%,接近CO_(2)平衡转化率(49.9%),同时,CO选择性和CO时空收率分别高达94.0%和423.1μmol·g^(-1)·s^(-1),且在100 h之内反应性能几乎没有衰减,具有优异的高温稳定性,此催化性能也超过了大多数文献报道。系列结构表征表明,Ir物种均匀地分散在α-Mo C载体上,其电子较利于转移至α-Mo C而形成金属载体强相互作用,极大地提高了催化稳定性;同时,当Ir负载量高于0.2%(质量分数)时,Ir团簇(Irn)和Ir单原子(Ir1)同时存在,与α-MoC形成了Irn-Ir1-C-Mo协同位点。其中,0.5%Ir/Mo C催化剂拥有较小尺寸的Irn和较多的Ir1,显著地促进了CO_(2)和H2的吸附和活化,并促进了甲酸盐中间体的生成和解离,从而获得了优异的RWGS性能。这项工作为设计和制备高效稳定的CO_(2)利用催化剂提供了一定的参考和指导。

Chemoselective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Ir-MoO_x/SiO_2 catalyst

In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different noble metals （Ir, Pt, Pd, Ru, Rh）, supports and Ir contents were screened. Among the investigated catalysts, 4 wt%Ir-MoOx/SiO2 with a Mo/Ir atomic ratio of 0.13 exhibited the best catalytic performance. The synergy between Ix particles and the partially reduced isolated MoOx species attached on them is essential for the excellent catalytic performance of Ix-MoOx/SiO2. The catalyst exhibited a better hydrogenolysis efficiency of THFA with the selectivity of 1,5-pentanediol of 65%-74% at a conversion of THFA of 70%-75% when the initial THFA concentration is ranging from 20 wt% and 40 wt%. And higher system pressure was also in favor of the conversion of THFA. During a stability test, the conversion of THFA and 1,5-pentanediol yield over Ix-MoOz/SiO2 decreased with reaction time, which can be explained by the leaching of Mo species during the reaction.

Preparation of novel Ni-Ir/γ-Al_2O_3 catalyst via high-frequency cold plasma direct reduction process

The novel Ni-Ir/γ-Al2O3 catalyst, denoted as NIA-P, was prepared by high-frequency cold plasma direct reduction method under ambient conditions without thermal treatment, and the conventional sample, denoted as NIA-CR, was prepared by impregnation, thermal calcination, and then by H2 reduction method. The effects of reduction methods on the catalysts for ammonia decomposition were studied, and they were characterized by XRD, N2 adsorption, XPS, and H2-TPD. It was found that the plasma-reduced NIA-P sample showed a better catalytic performance, over which ammonia conversion was 68.9%, at T = 450℃, P = 1 atm, and GHSV = 30, 000 h^-1. It was 31.7% higher than that of the conventional NIA-CR sample. XRD results showed that the crystallite size decreased for the sample with plasma reduction, and the dispersion of active components was improved. There were more active components on the surface of the NIA-P sample from the XPS results. This effect resulted in the higher activity for decomposition of ammonia. Meanwhile, the plasma process significantly decreased the time of preparing catalyst.

In-Situ FT-IR Investigation Methane to Syngas over of Partial Oxidation of Rh/SiO2 Catalyst

Partial oxidation of methane to syngas （POM） over Rh/SiO2 catalyst was investigated using in-situ FT-IR. When methane interacted with 1.0wt%Rh/SiO2 catalyst, it was dissociated to adsorbed hydrogen and CHx species. The adsorbed hydrogen atoms were transferred to SiO2 surface by ＂spill-over＂ and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO2 catalyst using in-situ FT-IR. It was found that CO2 was formed before CO could be detected when CH4 and O2 were introduced over the preoxidized Rh/SiO2 catalyst, whereas CO was detected before CO2 was formed over the prereduced Rh/SiO2 catalyst.

In Situ IR Spectroscopic Study on the Hydrogenation of 1,3-Butadiene on Fresh Mo_2C/γ-Al_2O_3 Catalyst

The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption on the Mo2C/γ-Al2O3 catalyst mainly forms π-adsorbed butadiene(πs and πd) and σ-bonded surface species. These species are adsorbed mainly on the surface Moδ+(0<δ<2) sites as evidenced by co-adsorption of 1,3-butadiene and CO on the fresh Mo2C/γ-Al2O3 catalyst. The IR spectrometric analysis show that hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst produces mainly butane coupled with a small portion of butene. The selectivity of butene during the hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst might be explained by the adsorption mode of adsorbed 1,3-butadiene. Additionally, the active sites of the fresh Mo2C/γ-Al2O3 catalyst may be covered by coke during the hydrogenation reaction of 1,3-butadiene. The treatment with hydrogen at 673 K cannot remove the coke deposits from the surface of the Mo2C/γ-Al2O3 catalyst.

IR AND EPR STUDIES OF THE NUCLEAR ALKYLATION OF TOLUENE AND ETHYLENE ON THE MODIFIED Mg—AND P—ZSM—5 CATALYST

The surface intermediate (C_2H_5^+ and CH_3C_6H_5^+) and the reactive pathway of nuclear alkylation of toluene with ethylene to para—ethyl toluene over Mg salt and phosphorus acid modified ZSM—5 zeolites have been studied by 1R and EPR methods.

Studies on the Hydrogenation of Acetonitrile over Fresh Mo_2C/γ-Al_2O_3 Catalyst by In-situ IR Spectroscopy

The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.

Study on Au/Al_2O_3 catalysts for low-temperature CO oxidation in situ FT-IR

Au/Al2O3 catalyst was prepared by a modified anion impregnation method and investigated with respect to its initial activity and stability for low-temperature CO oxidation.The activity changes of the catalyst were examined after separate treatment in CO＋O2 or CO2 ＋O2 .Furthermore,in situ FT-IR studies were performed to investigate the species on the surface when CO or CO＋O2 or CO2 ＋O2 was selected separately as adsorption gas.The results showed that Au/Al2O3 catalyst exhibited very high initial activity,but the catalytic activity was found to decrease gradually during CO oxidation with time on stream.And also,the activity of the catalyst declined after treatment in CO＋O2 or CO2 ＋O2 .The formation and accumulation of carbonate-like species during CO oxidation or treatment in CO＋O2 or CO2 ＋O2 might be mainly responsible for the activity decrease,which was reversible.

酸性环境下析氧反应Ir、Ru贵金属电催化剂的研究进展

水电解法是利用可再生能源生产氢气的最有效、最环保的方法之一。质子交换膜(PEM)水电解槽对可再生能源的储存和转化具有重要意义,与碱性电解水相比,具有设计紧凑、电压效率高和气体纯度高等优点。然而,阳极电催化剂的低效率、不稳定性和高成本阻碍了PEM水电解。许多析氧反应(OER)电催化剂在恶劣的酸性环境下,在OER电位作用下容易发生溶解或表面结构转变,最终导致催化性能急剧下降,因此酸性OER是阻碍PEM水电解槽实际应用的主要因素之一。高效、经济和耐用的电催化剂可降低OER的高动力学势垒,加速其反应动力学。迄今为止,Ir和Ru基纳米材料仍然代表着最先进的催化剂,已经设计和合成了多种先进的贵金属电催化剂,以增强酸性OER性能。本文综述了近5年性能优异的酸性OER新型电催化剂的研究进展。首先,讨论了对酸性OER的基本认识,包括其反应机理。在此基础上,对贵金属Ir、Ru单原子、合金和氧化物等方面综述了贵金属酸性OER电催化剂的设计和合成进展。最后,从反应机理研究和更高效的电催化剂设计等方面对酸性OER的未来发展提出了展望。

配体覆盖的Ir催化剂上巴豆醛加氢反应:金属-有机物界面促进活性和选择性

α,β-不饱和醇是药物和香料等精细化学品合成的重要中间体.在工业上将α,β-不饱和醛与强还原剂如NaBH_(4)等反应后可合成对应的不饱和醇,但该方法易导致环境污染等问题.α,β-不饱和醛选择性加氢制备α,β-不饱和醇是原子经济反应,符合绿色化学要求.但α,β-不饱和醛分子中含有共轭的C=C键和C=O键,在热力学和动力学上皆倾向于C=C键的加氢生成饱和醛,导致α,β-不饱和醇的选择性较低.因此提高α,β-不饱和醛中C=O的加氢选择性具有挑战性.巴豆醛属于典型的α,β–不饱和醛,其选择性加氢生成巴豆醇常作为模型反应用于研究催化剂构效关系.近年来,通过胶体方法制备配体保护的金属纳米颗粒在选择性加氢反应中表现出较好的选择性,可归因于配体产生的立体效应和电子效应等因素,但配体的存在往往抑制反应物在活性金属表面的吸附,从而导致反应活性下降.因此,如何克服活性-选择性的“跷跷板”瓶颈具有重要意义.本文以十四烷基三甲基溴化铵(TTAB)为保护剂,采用胶体法合成了Ir纳米颗粒,并将其负载在载体六方氮化硼上,获得一系列通过不同焙烧温度的催化剂,通过各种表征手段研究了催化剂结构和表面性质,并考察其在巴豆醛气相加氢反应中的性能.热重分析、原位漫反射红外光谱结果表明,尽管在制备过程中经过充分洗涤,催化剂表面仍有残留的TTAB存在,其含量随着焙烧温度的升高而减少,至500℃焙烧后彻底清除.TTAB覆盖在Ir表面,并产生了电荷转移.巴豆醛加氢反应结果表明,300℃焙烧的催化剂(Ir/BN-C3)具有最佳活性和选择性,其在准稳态条件下巴豆醇的选择性为94.4%,巴豆醇的生成转换频率(TOF)为0.02 s^(-1);而500℃焙烧的催化剂(Ir/BN-C5)上,巴豆醇的稳态选择性仅为56.2%,巴豆醇的生成TOF为0.004 s^(-1).动力学测试结果表明,与Ir/BN-C5相比,巴豆醛在Ir/BN-C3催化剂上具有更高的吸附平衡常数和更高的本征反应速率常数,表明TTAB的存在有效加强了巴豆醛在催化剂表面的吸附;另一方面,Ir-TTAB界面活性位比Ir-Ir活性位具有更高的本征活性,从而验证了Ir-TTAB界面在增强反应物吸附和促进反应速率方面起关键作用.但过高的TTAB表面覆盖度(例如在100℃焙烧的催化剂Ir/BN-C1中)会抑制H_(2)在催化剂表面的吸附,从而使反应速率降低.综上,合适的热处理条件可调节有机配体在催化剂上的含量及其与活性金属间的相互作用,从而同时提高反应活性和选择性,突破活性-选择性的“跷跷板”瓶颈,为高效选择性加氢催化剂的设计提供了新思路.

Ir/SiO_2上甲烷部分氧化制合成气反应的原位时间分辨红外和原位Raman光谱表征

采用原位时间分辨红外光谱和原位显微Raman光谱技术对Ir/SiO2 上甲烷部分氧化 (POM)制合成气反应的初级产物和反应条件下催化剂表面物种进行了跟踪考察 ,实验结果表明 ,在H2 预还原的新鲜Ir/SiO2 表面 ,CO是V(CH4)∶V(O2 )∶V(Ar) =2∶1∶45混合气反应的初级产物 ,因而甲烷的直接氧化过程是CO生成的主要途径 ;而在稳态反应条件下 ,CO生成的途径可能主要来自CO2 和H2 O与催化剂表面积碳物种 (CHx)和 /或CH4的反应 .催化剂上生成的积碳可能是导致稳态条件下Ir/SiO2 上POM反应机理不同于H2 预还原的新鲜催化剂的主要原因 .

钡修饰Ir/SiO_2催化剂对氨分解促进作用的研究

研究了浸渍法制备的Ba修饰S iO2担载型铱(Ir)基催化剂(Ba-Ir/S iO2)在氨催化分解模型反应的作用。结果表明Ba的添加显著提高了催化剂的活性和稳定性。采用H2-TPR和H2-TPD对Ba-Ir/SiO2进行分析和研究,结果显示助催化剂Ba和活性催化组分Ir之间发生了强相互作用。Ba-Ir/SiO2在氨催化分解模型反应中的主要活性物种是零价态的Ir。