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1.
刘海超  杨锡尧 《分子催化》1998,12(3):221-225
以水滑石焙烧而成的Mg-Al复合氧化物(Mg(Al)O)固体碱负载酞菁钴(CoPcTS)双功能催化剂催化1-辛硫醇氧化反应,具有与含10%NaOH的传统催化体系相催化性能,能有效地将1-辛硫醇氧化与二硫化合物,催化剂在循环使用时,活性下降可能与CoPcTS氧化中心聚集有关。  相似文献   

2.
以水滑石焙烧而成的Mg-Al复合氧化物(Mg(A1)O)固体碱负载磺化酞菁钴(CoPcTS)双功能催化剂催化1-辛硫醇氧化反应,具有与含10%NaOH的传统催化体系相似的催化性能,能有效地将1-辛硫醇氧化为二硫化合物.催化剂在循环使用时,活性下降,可能与CoPcTS氧化中心聚集有关.  相似文献   

3.
报导了酞菁钴负载到CuxS和CdS半导体办面合成的一种新型光催化剂,并对其光催化分解H2S的活性进行了考察,同时研究了酞菁 钴分子与半导体相互作用及其对催化性能的影响,实验结果表明,CoPc的负载能够显著提高复合硫化物催化剂光解H2S的活性,在一定条件下,能使反应速率提高2-3倍,活性的增加与CoPc加入量呈现非线性关系,且制备过程不同,催化剂活性的变化规律也不同。先负载到CuxS表面表现出更为明  相似文献   

4.
负载离子对型酞菁钴双功能硫醇氧化催化剂   总被引:2,自引:0,他引:2  
将分别带有正、负电荷基团的季铵盐酞菁钴CoPc[N(CH3 ) 3 I]4 和磺酸盐酞菁钴CoPc(SO3 Na) 4溶解在一起 ,负载在由水滑石热分解而成的MgAl复合氧化物碱性载体上 ,制成负载离子对型酞菁钴催化剂 ,其所具有的碱性、氧化性双功能的特征能够有效地催化 1 辛硫醇氧化 .当这两种酞菁钴配合物的摩尔比为 1时 ,催化活性最高 ,并且稳定性也有较明显的改善 .这种双功能催化剂体系具有酶催化的特点 ,即遵循双底物 ( 1 C8H17SH和O2 )Michaelis Menten动力学规律 ;表观活化能Ea=5 0 .4kJ·mol-1.在一定范围内提高二元酞菁钴混合物的负载量 ,单位酞菁钴中心的活性基本保持恒定 ,表明形成的二聚体络合物可在一定程度上抑制酞菁钴分子的聚集 ,改善催化剂的性能 .同时 ,增大Mg(Al)O载体量即碱中心数 ,有利于催化剂活性和稳定性的提高 .这类新型双功能催化剂具有工业应用的前景 .  相似文献   

5.
Co2(CO8)分别与4种硫代乙内酰脲S=CNHC(O)C(R1)(R2)N(COR3)反就,得到4个新的含硫代乙内酰脲桥基双齿配位的三核钴羰基硫族合物。用元素分析、IR、^1H NMR和MS等手段表征了它们的结构,用X射线衍射测定了其中一个族合物Co3(CO7)7(μ3-S)[μ,η^2-SCNC(O)C(CH3)(CH3)N(COCH3)](Ⅳ)的晶体结构,晶体属三斜晶系,P1↑-空间群,晶胞  相似文献   

6.
左霞  杨素苓 《合成化学》1998,6(2):208-210
以1,4-萘醌为原料,通过溴代,氰化和烷基化三步合成了1,4-二烷氧基萘-2,3-二腈(R=CH3(CH2)2-;CH3(CH2)3-;CH3CH2CH(CH3)-CH3(CH2)4,各产物用元素分析和红外光谱确证,与文献方法相比,本法简便有效。  相似文献   

7.
酞菁钴液相催化氧化羰基硫(COS)的研究   总被引:1,自引:0,他引:1  
本文首次报道在液相中,用金属酞菁催化氧化脱除羰基硫(COS)。发现COS先被水解成HS~-,HS~-再被氧化成S,酞菁钴(CoPC)的活性高于其它金属酞菁(MPC),酞菁苯环上推电子基因使酞菁的催化活性提高,双核酞菁钴的活性高子单核酞菁钴。D296树脂负载的酞菁钴的催化活性高于均相酞菁钴的活性。  相似文献   

8.
合成了四膦配体C(CH2PPh2)4,并研究了由钴-四膦配体组成的催化剂体系对烯烃氢甲酰化反应的催化作用.对反应的各种因素,如反应温度、反应压力、不同P/Co比,不同烯烃等的影响作了探讨,并与不同膦配体体系催化烯烃氢甲酰化作对比,发现膦配体催化活性有如下顺序:C(CH2PPh2)4≈Ph2P(CH2)2PPh2>Ph2P(CH2)3PPh2>Ph2PCH2PPh2>Ph2P(CH2)4PPh2.  相似文献   

9.
合成了两种以3-硝基邻苯二甲酸根为桥联配体的新型双核钴(Ⅱ)的配合物,即「o2(3PT)(Phen)4」。(ClO4)2.4H2O(配合物1)帮「Co2(3PT)NPhen)4」(ClO4)D2.5H2O(配合物2)。发现该两配合均具有较强的抑制人白血病细胞的活性。  相似文献   

10.
合成了三种以2-溴代对苯二甲酸为桥联配体的新型双核钴(Ⅱ)的配合物,即[Co2(BTP)(phen)4](ClO4)2.H2O(配合物1)、[Co2(BTP)(Nphen)4](ClO4)2.2H2O(配合物2)和[Co2(BTP)(Bpy)4]ClO4)2,2HO(配合物3)(BTP=2-溴代对苯二甲酸根,phen=1,10-菲罗啉,Nphen=5-硝基-1,10-菲罗啉,Bpy-2,2'联吡啶  相似文献   

11.
Mercaptans in petroleum products wreck the quality of finished products, so it is necessary to remove them in petroleum refining industry. Merox fixed-bed process is widely used in which mercaptans are converted by contacting feedstock with a metal phthalocyanine catalyst in the presence of air and an alkaline agent. However, use of caustic brings a spent caustic disposal problem so that novel caustic-free catalysts are highly desired to meet environment requirements1-3. It is not just simply …  相似文献   

12.
Cobalt phthalocyanine (CoPc) complexes in the presence of caustic are widely used in the refining industry for sweetening (i. e. the catalytic oxidation of mercaptans to disulfides) of petroleum products[1]. However, the use of caustic leads to the environmental and economic disadvantages because the spent caustic is recognized as a hazardous material. To set up a more environmentally friendly process, Holmgren et al. and Liu et al. recently reported that bifunctional mixed Mg-Al oxide (denoted as Mg(Al)O)-supported CoPc catalysts, which possess oxidation sites and basic sites, can effectively oxidize mercaptans to disulfides[2,3]. But for these catalysts, we found that the formation of CoPc aggregates on Mg(Al)O during the autoxidation led to their deactivation.3 It is known that the aggregation can be inhibited by anchoring CoPc to supports, such as TiO2 and SiO2, modified with organic functional groups. However,it is unknown whether the basic Mg(Al)O materials can be functionalized with organic compounds with no damage to their basic sites. Here we report the preparation of a novel bifunctional catalysts of cobalt tetraaminophthalocyanine CoPc(NH2)4 covalently bound to Mg(Al)O modified with a organosilane, as well as their catalytic performance in mercaptan autoxidation.  相似文献   

13.
Developing copper-free catalysts for CO2 conversion into hydrocarbons and oxygenates is highly desirable for electrochemical CO2 reduction reaction (CO2RR). Herein, we report a cobalt phthalocyanine (CoPc) and zinc–nitrogen–carbon (Zn-N-C) tandem catalyst for CO2RR to CH4. This tandem catalyst shows a more than 100 times enhancement of the CH4/CO production rate ratio compared with CoPc or Zn-N-C alone. Density functional theory (DFT) calculations and electrochemical CO reduction reaction results suggest that CO2 is first reduced into CO over CoPc and then CO diffuses onto Zn-N-C for further conversion into CH4 over Zn-N4 site, decoupling complicated CO2RR pathway on single active site into a two-step tandem reaction. Moreover, mechanistic analysis indicates that CoPc not only generates CO but also enhances the availability of *H over adjacent N sites in Zn-N4, which is the key to achieve the high CH4 production rate and understand the intriguing electrocatalytic behavior which is distinctive to copper-based tandem catalysts.  相似文献   

14.
以钛酸正丁酯为原料采用原位化学合成的新方法,以二价钴离子为模板剂在TiO2凝胶基质合成的同时,通过邻苯二腈的四聚反应将酞菁钴(CoPc)在TiO2表面原位合成,得到均匀掺杂的CoPc/TiO2光催化剂,用紫外-可见漫反射光谱、傅立叶变换-红外光谱等证实了CoPc的成功负载,并将其用于可见光下、水溶液中CO2的还原反应,通过比较还原反应的效率,确定此光催化剂的最佳制备条件为:CoPc在TiO2表面的摩尔负载量为3%,焙烧温度为200℃,溶胶搅拌时间为20 h,钛酸丁酯与邻苯二腈及钴离子同时加入溶胶体系中,采用此法制备的催化剂中CoPc酞菁环上的电子密度增加,有利于作为敏化剂的激发态CoPc向半导体TiO2的导带注入电子,而且CoPc被均匀分散于TiO2凝胶基质中,其上的“笼效应”有效避免了CoPc的迁移,使其二聚及多聚倾向大大减弱,此光催化剂用于CO2光还原,在可见光照射下,水溶液中即可光还原CO2为甲醇、甲醛、甲酸等产物,在光照反应10 h后总产量最高可达2903.83μmol/ g-catal。  相似文献   

15.
Namba K  Wang J  Cui S  Kishi Y 《Organic letters》2005,7(24):5421-5424
[reaction: see text] With use of 1 mol % of Cr catalyst 5, surprisingly efficient Cr-mediated couplings of aldehydes with various types of nucleophiles have been realized. The catalyst set of Cr catalyst 5 and Ni catalyst 4 is used for alkenylation, alkynylation, and arylation, whereas the catalyst set of Cr catalyst 5 and CoPc (cobalt phthalocyanine) is used for 2-haloallylation, alkylation, and propargylation. Only the Cr catalyst 5 is required for allylation. The reaction rates in DME and THF have been found significantly faster than that in MeCN.  相似文献   

16.
Carbon-supported metallophthalocyanine catalysts, composed of a transition central metal M (M = Co, Mn, Ni, Fe) in the phthalocyanine ring, were synthesized in this work. As cathodic reaction in a fuel cell, the oxygen reduction reaction (ORR) was investigated in alkaline medium with linear scanning voltammetry at the surface of these electrocatalysts deposited onto a rotating disk electrode (RDE). It was found that the number of electrons transferred depended on the nature of the metallic cation in the catalyst. Evidences provided with Koutecky-Levich approach showed that iron phthalocyanine (FePc) exhibited the better electrocatalytic ability toward the ORR with four electrons exchanged and low activation overpotential. Among these different as-prepared materials, MnPc and FePc led to a four-electron pathway, while CoPc and NiPc proceeded by a two-electron route. The latter reaction process was also determined with a rotating ring-disk electrode (RRDE), which allowed the determination of hydrogen peroxide formed as O2 reduction intermediate in a small amount, i.e., less than 1.2 %.  相似文献   

17.
合成气直接制二甲醚双功能催化剂助剂的研究   总被引:16,自引:1,他引:16  
葛庆杰  黄友梅 《分子催化》1998,12(4):308-311
合成气直接制二甲醚较间接法制取二甲醚有显著的经济效益和重要的理论意义,因而日益引起人们的重视[1].其核心是研制兼有甲醇合成和脱水两种功能的催化剂,即在催化剂中同时含有这两种功能的活性组分.目前采用的催化剂体系多为铜锌氧化物和酸性脱水组分组成的复合催...  相似文献   

18.
The autoxidation of cumene to cumene hydroperoxide (CHP) in the presence of catalyst which was prepared by adsorbing copper(II) acetate onto polymer support, was investigated. When a styrene-divinylbenzene copolymer with sulfonic acid functional groups was used as a support, the resulting catalyst had no catalytic activity. When a macroreticular acrylic polymer containing carboxylic acid exchange groups was used as a support, an effective catalyst was obtained. In the presence of this catalyst (0.2 g Cu(OAc)2-BR-0.6 per 10 mL of cumene) at 353 K, the steady autoxidation rate is 84% faster than that initiated with CHP; the selectivity is 99% at 6.8% conversion. The catalyst is stable at 383 K. Furthermore, the catalyzed cumene autoxidation rate increases linearly with copper acetate loading as well as the amount of catalyst. But when the steady autoxidation rate increases, the selectivity to cumene hydroperoxide reduces, but is still satisfactory. Hence, it is possible to speed up the cumene autoxidation rate by raising the reaction temperature, using catalysts with high metal loading and using more catalyst.  相似文献   

19.
New graphene oxide (GO)‐tethered–CoII phthalocyanine complex [CoPc–GO] was synthesized by a stepwise procedure and demonstrated to be an efficient, cost‐effective and recyclable photocatalyst for the reduction of carbon dioxide to produce methanol as the main product. The developed GO‐immobilized CoPc was characterized by X‐ray diffraction (XRD), FTIR, XPS, Raman, diffusion reflection UV/Vis spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP‐AES), thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). FTIR, XPS, Raman, UV/Vis and ICP‐AES along with elemental analysis data showed that CoII–Pc complex was successfully grafted on GO. The prepared catalyst was used for the photocatalytic reduction of carbon dioxide by using water as a solvent and triethylamine as the sacrificial donor. Methanol was obtained as the major reaction product along with the formation of minor amount of CO (0.82 %). It was found that GO‐grafted CoPc exhibited higher photocatalytic activity than homogeneous CoPc, as well as GO, and showed good recoverability without significant leaching during the reaction. Quantitative determination of methanol was done by GC flame‐ionization detector (FID), and verification of product was done by NMR spectroscopy. The yield of methanol after 48 h of reaction by using GO–CoPc catalyst in the presence of sacrificial donor triethylamine was found to be 3781.8881 μmol g?1 cat., and the conversion rate was found to be 78.7893 μmol g?1cat. h?1. After the photoreduction experiment, the catalyst was easily recovered by filtration and reused for the subsequent recycling experiment without significant change in the catalytic efficiency.  相似文献   

20.
The precise control of electronic configurations of catalytic sites via molecular engineering is significantly desirable for boosting electrocatalytic activity. We reported a new-type composite electrocatalyst with cobalt phthalocyanine supported on N-doped MXene nanosheets (N-MXene/CoPc) through a self-assembly process. Beneficial from the joint action of N sites participation and axial coordination, N-MXene/CoPc exhibits a high ORR activity with positive onset potential (Eonset=0.98 V vs. RHE) and half-wave potential (E1/2=0.863 V), which is superior over the pristine CoPc (E1/2=0.72 V) and the composite with undoped MXene as support (MXene/CoPc, E1/2=0.771 V). Additionally, N-MXene/CoPc exhibits an excellent durability with only 8.5 % attenuation after 25000 s of continuous i-t test, while a more obvious decay 18.6 % for 20 wt.% Pt/C. This work not merely reported a robust ORR catalyst, but more provides a reasonable design strategy for nonnoble-metal catalysts through catalyst-support interactions.  相似文献   

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