CN102039131B - Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof - Google Patents

Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof Download PDF

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CN102039131B
CN102039131B CN 201110003168 CN201110003168A CN102039131B CN 102039131 B CN102039131 B CN 102039131B CN 201110003168 CN201110003168 CN 201110003168 CN 201110003168 A CN201110003168 A CN 201110003168A CN 102039131 B CN102039131 B CN 102039131B
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oxide
catalyst
water
hydrogen
eosin
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CN102039131A (en
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张静
赵雪伶
康诗钊
李向清
穆劲
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华东理工大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources
    • Y02E60/364Hydrogen production from non-carbon containing sources by decomposition of inorganic compounds, e.g. splitting of water other than electrolysis, ammonia borane, ammonia

Abstract

本发明提供一种用于可见光催化还原水制氢的催化剂及其制备方法,每100mg所述催化剂中含有10-60mg曙红Y、35-85mg碳纳米管和1-10mg氧化物。 The present invention provides a catalyst for the visible light and a catalytic hydrogen reduction preparation method, each of said catalyst containing 10-60mg 100mg Eosin Y, 35-85mg 1-10mg carbon nanotubes and an oxide. 通过本发明的上述技术方案,利用曙红作为敏化剂,碳纳米管作为载体和光生电子通道,氧化铜等氧化物作为助催化剂,实现了可见光催化还原水制氢。 By the above-described aspect of the present invention, using Eosin as sensitizer, and carbon nanotubes as carriers photogenerated electron ducts, copper oxides such as co-catalyst, to achieve a visible catalytic reduction of water to hydrogen. 本催化剂在可见光照射下,具有较高的制氢活性,可用于可见光催化还原水制取氢气。 This catalyst under visible light irradiation, hydrogen having a higher activity, can be used for the catalytic reduction of visible water to produce hydrogen. 并且利用氧化物代替Pt作为助催化剂,实现了催化剂的非铂化。 Instead of Pt and an oxide as a promoter, to achieve a non-platinum catalyst.

Description

—种用于可见光催化还原水制氢的催化剂及其制备方法技术领域[0001] 本发明涉及太阳能制氢领域,特别涉及一种用于可见光催化还原水制氢的催化剂及其制备方法。 - kind of visible light for the catalytic reduction catalyst and preparation BACKGROUND Hydrogen Production [0001] The present invention relates to a solar hydrogen generation, and in particular relates to a catalyst and a preparation method for the catalytic reduction of visible hydrogen production from water. 背景技术[0002]目前,地球上的资源已无法长久满足人们的需求,并且化石燃料的使用造成了很大的环境污染。 [0002] Currently, the resources of the earth has been unable to meet long-term needs of people, and the use of fossil fuels has created a significant environmental pollution. 太阳能和氢能被认为是解决以上问题的最有效途径。 Solar and hydrogen energy is considered to be the most effective way to solve the above problems. 太阳能供应的不稳定性使其直接利用受到了很大的限制。 Instability of supply of solar energy into direct use has been greatly restricted. 如果可以利用太阳能制氢,将太阳能转变为氢能,便可克服太阳能的不稳定性。 If hydrogen can use solar energy, the solar energy into hydrogen energy, solar energy can overcome the instability. 这样的太阳能-氢能系统,将是未来解决能源利用和生态环境问题的有效途径之一。 Such a solar - hydrogen energy system will be one of the effective ways to solve future energy use and ecological problems. [0003] 人们对太阳能制氢方法的研究主要集中在直接热分解法、热化学循环法、光催化法以及光电化学分解法四个方面。 [0003] The method of solar hydrogen research people focused on four aspects of the direct thermal decomposition method, a thermal chemical recycling method, photocatalytic decomposition method, and photoelectrochemical. 其中,光催化法以及光电化学分解法所需装置简单、反应条件温和,是制氢的理想方法。 Wherein the desired light and photoelectrochemical catalytic decomposition device is simple, mild reaction conditions, the ideal method of hydrogen production. 引起了科技工作者的广泛兴趣,已成为太阳能制氢领域的前沿和热点。 Attracted wide interest in science and technology workers, it has become a cutting-edge field of solar energy and hot hydrogen. 目前,人们已获得了在紫外区具有很高活性的制氢材料。 At present, people have obtained materials with high hydrogen production activity in the ultraviolet region. 但是,这些材料的带隙较宽,不吸收可见光。 However, a wide band gap of these materials, does not absorb visible light. 而太阳光谱的大部分落在可见光区,所以这些材料的太阳能利用效率很低。 And most of the visible region of the solar spectrum falls, so the low efficiency of solar energy utilization of these materials. 因此,获得在可见光区具有高活性的制氢材料是各国科技工作者所共同关注的焦点。 Thus, a material with a high hydrogen production activity in the visible region is the focus of national science and technology workers of common concern. 最近,人们受染料敏化太阳能电池研究的启发,对染料敏化光催化剂进行了探讨。 Recently, it was inspired by the solar cell research Dye, dye-sensitized photocatalyst discussed. 结果表明这有可能成为获得高效可见光制氢催化剂的新途径。 The results indicate that this may be a new way to obtain high visible light hydrogen production catalysts. 染料敏化剂的引入大大拓宽了催化剂设计时的选择面,对于今后开发新型太阳能制氢材料具有重要意义,应得到人们的重视。 The introduction of a dye sensitizer greatly expanded choices when designing catalyst for the future development of new solar hydrogen production materials is important, it should get people's attention. 这方面的研究目前还不成熟,仍有许多问题需要解决。 Research in this area is not yet mature, there are still many problems to be solved. 此外,为了提高制氢效率,人们通常采用Pt等贵金属来抑制光生载流子的复合。 In order to improve the efficiency of hydrogen production, it is usually a noble metal such as Pt to suppress recombination of photogenerated carriers. 由于我国Pt等贵金属资源十分贫乏,这意味着负载Pt等贵金属的光催化剂在我国不能大规模应用,否则会对我国的经济安全、国家安全造成严重隐患。 Because of Pt and other precious metal resources are very poor, light catalytic noble metal such as Pt which means that the load can not be large-scale application in our country, or else the country's economic security, national security posed serious risks. 所以,寻找一种廉价的替代Pt等贵金属的助催化剂对于我国太阳能制氢技术的实际应用意义十分重大。 So, look for a co-catalyst precious metal such as Pt is an inexpensive alternative to very major significance for the practical application of solar hydrogen technology in China. 综上所述,设计并开发一个用于可见光催化还原水制氢的敏化剂、碳纳米管和氧化物催化剂对于光催化还原水制氢在实际中的大规模应用具有十分重要的意义。 In summary, the design and development of a catalytic reduction of water to hydrogen for visible sensitizer, carbon nanotubes and the oxide catalyst is very important for large-scale application of photocatalytic reduction of water to hydrogen in practice. 发明内容[0004] 本发明的目的是提供一种用于可见光催化还原水制氢的催化剂,利用廉价的氧化物来替代现有技术中的Pt等贵金属。 SUMMARY OF THE INVENTION [0004] The object of the present invention is to provide a method for catalytic reduction catalyst visible hydrogen production from water, using an inexpensive alternative to the prior art, an oxide of a noble metal such as Pt. [0005] 为了解决上述技术问题,本发明采用如下方案:[0006] 一种用于可见光催化还原水制氢的催化剂,每IOOmg所述催化剂中含有10-60mg 曙红Y、35_85mg碳纳米管和I-IOmg氧化物。 [0005] To solve the above problems, the present invention adopts the following scheme: [0006] A visible-catalytic reduction catalyst for hydrogen production from water, each of said catalyst containing 10-60mg IOOmg Eosin Y, 35_85mg carbon nanotubes and I-IOmg oxide. [0007] 所述氧化物选自氧化铜、氧化镍、氧化亚铁、三氧化二铁、四氧化三铁和三氧化二铬。 The [0007] oxide selected from copper oxide, nickel oxide, ferrous oxide, ferric oxide, triiron tetroxide, and chromium oxide. [0008] 所述氧化物为氧化铜。 [0008] The oxide is copper oxide. [0009] 所述催化剂中的曙红Y、碳纳米管和氧化铜的质量比为O. 5 : I : 0.06。 [0009] The mass of the catalyst in the eosin Y, a carbon nanotube and copper oxide ratio of O. 5: I: 0.06. [0010] 所述氧化物为氧化铁。 The [0010] oxide is iron oxide. [0011] 所述催化剂中的曙红Y、碳纳米管和氧化铁的质量比为1.25 : I : 0.005。 Eosin Y of the [0011] catalyst, carbon nanotubes and iron oxide mass ratio of 1.25: I: 0.005. [0012] 一种制备所述的用于可见光催化还原水制氢的催化剂的方法,其特征在于,首先制备碳纳米管-金属盐前驱体;将所述前驱体放入马弗炉中,空气气氛下,200-40(TC下煅烧数小时,得到碳纳米管-金属氧化物体系;将所述碳纳米管-金属氧化物体系放入曙红Y 的水溶液中N2保护下浸泡,分离,得到所述的催化剂。[0013] 通过本发明的上述技术方案,利用曙红作为敏化剂,碳纳米管作为载体和光生电子通道,氧化铜等氧化物作为助催化剂,实现了可见光催化还原水制氢。本催化剂在可见光照射下,具有较高的制氢活性,可用于可见光催化还原水制取氢气。并且利用氧化物代替Pt 作为助催化剂,实现了催化剂的非钼化。附图说明[0014] 图I (a)根据本发明的一个优选实施例的CuO的标准XRD图,(b)多壁碳纳米管的XRD图,(c)多壁碳纳米管-CuO体系的XRD图。[0015] 图2是 [0012] A process for preparing a catalyst for catalytic processes visible reduction of water into hydrogen, characterized in that, firstly preparing a carbon nanotube - metal salt precursor; the precursor is placed in a muffle furnace in air atmosphere, 200-40 (TC calcined for several hours, the carbon nanotube - metal oxide systems; the carbon nanotube - metal oxide systems into an aqueous solution of eosin Y under N2 protection of soaking, isolated, to give said catalyst. [0013] by the above aspect of the present invention, using eosin as sensitizer, and carbon nanotubes as carriers photogenerated electron ducts, copper oxides such as co-catalyst, catalytic reduction achieved visible water system hydrogen. this catalyst under visible light irradiation, hydrogen having a higher activity, can be used for the catalytic reduction of visible water to produce hydrogen. Pt and an oxide as a cocatalyst in place, to achieve a non-molybdenum catalyst. BRIEF DESCRIPTION oF dRAWINGS [0014 standard XRD pattern of CuO] FIG I (a) in accordance with a preferred embodiment of the present invention, (b) XRD FIG MWCNTs, (c) a multi-walled carbon nanotubes XRD pattern -CuO system. [0015 ] Figure 2 is a 据本发明的一个优选实施例的多壁碳纳米管-CuO (6% )体系的TEM照片。[0016] 图3是根据本发明的一个优选实施例的多壁碳纳米管-Cu0(6% )体系的XPS谱。[0017] 图4是根据本发明的一个优选实施例的曙红Y、碳纳米管和氧化铜集成体系(质量比为O. 5 : I : O. 06)的FT-IR 谱。具体实施方式[0018] 下面结合附图,给出本发明的较佳实施例,并予以详细描述,使能更好地理解本发明的功能、特点。[0019] 本发明利用曙红作为敏化剂,碳纳米管作为载体和光生电子通道,氧化铜等氧化物作为助催化剂,构筑了催化剂。解决了可见光还原水制氢及Pt助催化剂替代的问题,得到了具有较高制氢效率的可见光催化体系。[0020] 根据本发明的催化剂的组成为:每IOOmg催化剂含有10-60mg曙红Y、35_85mg碳纳米管、I-IOmg氧化物助催化剂。[0021] 根据本发明的一个优选实施例,所述氧化物助催化 According to TEM photograph MWNT -CuO (6%) of a system of the preferred embodiment of the present invention. [0016] FIG. 3 is a multi-walled carbon nanotubes -Cu0 (6% in accordance with a preferred embodiment of the present invention. ) system of the XPS spectra of [0017] FIG. 4 is a eosin Y a preferred embodiment of the present invention, an integrated system of a carbon nanotube and copper oxide (mass ratio of O. 5:. I: O. 06) of FT- IR spectrum. dETAILED dESCRIPTION [0018] dRAWINGS given preferred embodiment of the present invention, and be described in detail, to enable a better understanding of the functions of the present invention, the characteristics. [0019] the present invention utilizes eosin as the sensitizer, carbon nanotubes as a carrier channel and the photogenerated electrons, copper oxides such as co-catalyst, a catalyst constructed solve the problem of reduction of water to hydrogen and visible Pt alternative cocatalyst to obtain hydrogen having a high the present invention is a catalyst containing 10-60mg per IOOmg eosin Y, 35_85mg nanotubes, I-IOmg oxide cocatalyst [0021] according to: visible light efficiency catalytic system [0020] the composition of the catalyst of the present invention is. embodiment, the catalytic promoter oxides preferred embodiment 选自氧化铜、氧化镍、氧化亚铁、三氧化二铁、四氧化三铁、三氧化二铬。[0022] 制备本发明的催化剂所需药品包括:曙红Y :5-100mg ;碳纳米管:20_100mg ;金属盐:0. 01-0. Imol,金属盐指的是铜、镍、钴、铁、铬的氯化物、硫酸盐、硝酸盐、醋酸盐等。[0023] 根据本发明的催化剂的制备工艺包括:(I)将碳纳米管、金属盐的水溶液加入到烧杯中,然后用水稀释至预定体积。室温下搅拌数小时后,将水蒸干得到碳纳米管-金属盐前驱体。 A compound selected from copper oxide, nickel oxide, ferrous oxide, ferric oxide, triiron tetroxide, chromium trioxide [0022] The catalyst prepared in the present invention the desired drug comprising: Eosin Y: 5-100mg; nanocarbon tube: 20_100mg; salts:.. 0 01-0 Imol, it refers to a metal salt of copper, nickel, cobalt, iron, chromium chloride, sulfate, nitrate, acetate, etc. [0023] according to the present invention. the catalyst preparation process comprises: (I) a carbon nanotube, a metal salt aqueous solution was added to the beaker, then diluted with water to a predetermined volume after stirring for several hours at room temperature, water was evaporated to dryness to give a carbon nanotube - metal precursor. body. (II)将得到的前驱体放入马弗炉中,空气气氛下,200-400°C下煅烧数小时,得到碳纳米管-金属氧化物体系。 (II) The obtained precursor placed in a muffle furnace under air atmosphere, calcined for several hours at 200-400 ° C, the carbon nanotube - metal oxide systems. (III)将该碳纳米管-金属氧化物体系放入曙红Y的水溶液中N2保护下浸泡20min-24h,分离,得到曙红Y、碳纳米管和氧化物催化剂。 (III) The carbon nanotube - the system into an aqueous solution of a metal oxide of Eosin Y N2 protection soaking 20min-24h, separated to obtain eosin Y, carbon nanotubes and an oxide catalyst. [0024] 实施例I[0025] 将80mg碳纳米管、O. 6mL O. Imol · L—1的硝酸铜水溶液加入到IOOmL烧杯中,用水稀释至20mL。 [0024] Example I [0025] The carbon nanotubes 80mg, O. 6mL O. Imol · L-1 was added to an aqueous solution of copper nitrate IOOmL beaker and diluted with water to 20mL. 室温下搅拌Ih后,将水蒸干得到碳纳米管-金属盐前驱体。 After stirring for Ih at room temperature, water was evaporated to dryness to give a carbon nanotube - metal precursor. [0026] 将得到的前驱体放入马弗炉中,空气气氛下,300°C下煅烧3h,得到碳纳米管-氧化铜体系。 [0026] The resulting precursor placed in a muffle furnace under air atmosphere, calcined at 300 ° C 3h, the carbon nanotube - copper oxide system. CuO的标准X射线衍射XRD谱图如图I (a)所示;多壁碳纳米管的XRD图谱如图I (b)所示;碳纳米管-氧化铜体系的XRD图谱如图I (c)所示。 CuO standard X-ray diffraction XRD spectrum of FIG. I (a) below; MWNTs XRD pattern of FIG. I (b) below; carbon nanotube - XRD pattern of copper oxide system was shown in I (c ) shown in FIG. 另外,图2示出了碳纳米管-氧化铜体系的透射电子显微镜TEM照片;图3示出了碳纳米管-氧化铜体系的X射线光电子能谱分析XPS谱。 Further, FIG. 2 shows a carbon nanotube - a transmission electron microscope TEM photograph of copper oxide system; FIG. 3 shows a carbon nanotube - X-ray photoelectron spectroscopy XPS spectra of copper oxide system. [0027] 将60mg碳纳米管-氧化铜体系放入到60mL曙红Y的溶液中(lmg/mL),在N2保护下浸泡30min,得到曙红Y、碳纳米管和氧化铜催化剂,其FT-IR谱如图4所示。 [0027] The carbon nanotube 60mg - copper oxide system was put into 60mL of eosin Y (lmg / mL), under N2 protection for 30min to give eosin Y, carbon nanotubes and copper oxide catalyst FT -IR spectra shown in FIG. [0028] 实施例2[0029] 将85mg碳纳米管、O. 4mL O. Imol · Γ1的硝酸铜水溶液加入到IOOmL烧杯中,用水稀释至20mL。 [0028] Example 2 [0029] The carbon nanotubes 85mg, O. 4mL O. Imol · Γ1 aqueous copper nitrate solution was added to IOOmL beaker and diluted with water to 20mL. 室温下搅拌Ih后,将水蒸干得到碳纳米管-金属盐前驱体。 After stirring for Ih at room temperature, water was evaporated to dryness to give a carbon nanotube - metal precursor. (II)将得到的前驱体放入马弗炉中,空气气氛下,300°C下煅烧3h,得到碳纳米管-氧化铜体系。 (II) The obtained precursor placed in a muffle furnace under air atmosphere, calcined at 300 ° C 3h, the carbon nanotube - copper oxide system. (III)将上述碳纳米管-氧化铜体系放入到IOmL曙红Y的溶液中(lmg/mL),在N2保护下浸泡30min, 得到曙红Y、碳纳米管和氧化铜催化剂。 (III) the carbon nanotube - IOmL solution was placed in Eosin Y (lmg / mL) copper oxide system, under N2 protection soaked in 30min, to give eosin Y, carbon nanotubes and copper oxide catalyst. [0030] 实施例3[0031] 将35mg碳纳米管、O. 4mL O. Imol · L—1的硝酸铜水溶液加入到IOOmL烧杯中,用水稀释至20mL。 3 [0031] [0030] Example embodiments will 35mg nanotubes, O. 4mL O. Imol · L-1 was added to an aqueous solution of copper nitrate IOOmL beaker and diluted with water to 20mL. 室温下搅拌Ih后,将水蒸干得到碳纳米管-金属盐前驱体。 After stirring for Ih at room temperature, water was evaporated to dryness to give a carbon nanotube - metal precursor. (II)将得到的前驱体放入马弗炉中,空气气氛下,300°C下煅烧3h,得到碳纳米管-氧化铜体系。 (II) The obtained precursor placed in a muffle furnace under air atmosphere, calcined at 300 ° C 3h, the carbon nanotube - copper oxide system. (III)将上述碳纳米管-氧化铜体系放入到60mL曙红Y的溶液中(lmg/mL),在N2保护下浸泡30min, 得到曙红Y、碳纳米管和氧化铜催化剂。 (III) the carbon nanotube - placed in a 60mL solution of eosin Y (lmg / mL) copper oxide system, under N2 protection soaked in 30min, to give eosin Y, carbon nanotubes and copper oxide catalyst. [0032] 实施例4[0033] (I)将实施例I中得到的曙红Y、碳纳米管和氧化铜催化剂、三乙醇胺溶液(2. 5-20 % V/V)放入光催化制氢装置中。 [0032] Example 4 [0033] (I) The embodiment Eosin Y obtained in Example I, carbon nanotubes and copper oxide catalyst, triethanolamine (2. 5-20% V / V) into the optical catalysis It means hydrogen. 将溶液pH调节为4-13后,在暗处搅拌下通N2 30min以赶走体系中的O2。 The solution was adjusted to pH 4-13 under stirring in the dark for 30 min to drive off through the system N2 of the O2. [0034] (II)将集气装置充满水后,打开光源,在滤光片存在的情况下开始制氢。 [0034] (II) after the gas collection device is filled with water, turn the light source, in the presence of hydrogen began filter. 反应温度为20-70 °C。 The reaction temperature is 20-70 ° C. [0035] (III)反应数小时后,关闭光源,用N2将制氢装置中的H2吹扫到集气装置中。 [0035] After (III) for several hours, turn off the light source, the hydrogen plant with N2 H2 of purge gas to the collection means. 待吹扫完全后,用气相色谱检测H2的含量。 After fully purged, the content of H2 was detected by gas chromatography. [0036] 具体实施步骤如下:[0037] (a)将90mg曙红Y、碳纳米管和氧化铜集成体系(质量比为O. 5 : I : O. 06)以及60mL体积分数为5 %的三乙醇胺溶液放入自制的光催化制氢评价装置中,调节pH到11, 暗处搅拌下通N2 30min以赶走体系中的02。 [0036] In particular embodiments the steps of: [0037] (a) a 90mg Eosin Y, system integration of carbon nanotubes and copper oxide (mass ratio of O. 5: I: O. 06) and 60mL of 5% of the volume fraction Photocatalytic hydrogen production evaluation apparatus triethanolamine solution was placed in the self-adjusted to pH 11, the dark mixture was stirred at 02 to drive off the through N2 30min system. [0038] (b)将集气装置充满水后,打开光源开始制氢,反应温度为45°C。 [0038] (b) after the gas collection device is filled with water, began to open the hydrogen source, the reaction temperature was 45 ° C. 光源为1000W的卤钨灯,光源距光催化制氢装置的距离为16cm。 1000W is a tungsten-halogen light source, the distance from the light source means hydrogen catalyst is 16cm. 光源与反应器之间加装滤光片以滤去波长小于420nm的紫外光。 Installation of filters between the light source and the reactor to filter the ultraviolet wavelength of less than 420nm. [0039] (c)反应3h后,关闭光源,用N2将制氢装置中产生的H2吹扫到集气装置中。 [0039] (c) reaction 3h, off the light source, H2 with N2 generated in the hydrogen plant purge gas to the collection means. 待吹扫完全后,用气相色谱检测H2的含量。 After fully purged, the content of H2 was detected by gas chromatography. 得到该催化剂的制氢速度可达I. ISmmol .g'气相色谱相关参数:柱箱温度:35°C ;TCD检测器温度:60°C ;进样器温度:100°C ;电流:50mA ;旋钮圈数:4圈。 Hydrogen production rate of the catalyst obtained reach I. ISmmol .g 'GC parameters: oven temperature: 35 ° C; TCD detector temperature: 60 ° C; Injector temperature: 100 ° C; Current: 50mA; knob turns: 4 turns. [0040] 根据本发明的实施例2或3中得到的曙红Y、碳纳米管和氧化铜催化剂的析氢速率接近O。 [0040] The eosin Y Example 2 or 3 of the present invention is obtained, the rate of hydrogen evolution of the carbon nanotubes and copper oxide catalyst proximity O. [0041] 根据本发明的另一个优选实施例的曙红Y、碳纳米管和氧化镍催化剂的析氢速率为49. 72ymole · g-1 · h'其中曙红Y :碳纳米管:氧化镍=I : I : O. Ol0[0042] 根据本发明的又一个优选实施例的曙红Y、碳纳米管和氧化铁催化剂的析氢速率为2. 524ymole · g'h'其中曙红Y :碳纳米管:氧化铁=I. 25 : I : 0.005。 [0041] The Eosin Y another preferred embodiment of the present invention, carbon nanotubes and the rate of hydrogen evolution catalyst is nickel oxide 49. 72ymole · g-1 · h 'Eosin Y wherein: carbon nanotubes: NiO = I: I: O. Ol0 [0042] according to yet another embodiment of the eosin Y preferred embodiment of the present invention, the rate of hydrogen evolution catalyst is iron oxide and carbon nanotubes 2. 524ymole · g'h 'wherein eosin Y: nanocarbon tube: iron = I 25:. I: 0.005. [0043] 以上所述的,仅为本发明的较佳实施例,并非用以限定本发明的范围,本发明的上述实施例还可以做出各种变化。 [0043] The above are only preferred embodiments of the present invention is not intended to limit the scope of the present invention, the above-described embodiments of the present invention, various modifications may be made. 即凡是依据本发明申请的权利要求书及说明书内容所作的简单、等效变化与修饰,皆落入本发明专利的权利要求保护范围。 I.e., all according to the present invention as claimed in the claims and specification disclosure content made by simple modifications and equivalent arrangements, the present invention are claimed in the patent falls within the scope of claims. 本发明未详尽描述的均为常规技术内容。 No detailed description of the present invention are conventional technical contents.

Claims (5)

1. 一种用于可见光催化还原水制氢的催化剂,其特征在于,每IOOmg所述催化剂中含有10-60mg曙红Y、35-85mg作为载体和光生电子通道的碳纳米管和Ι-lOmg氧化物,所述氧化物选自氧化铜、氧化镍、氧化亚铁、三氧化二铁、四氧化三铁和三氧化二铬。 1. A visible-catalytic reduction catalyst for hydrogen production from water, characterized in that each of said catalyst containing 10-60mg IOOmg Eosin Y, 35-85mg as a carrier channel and photogenerated electrons and carbon nanotubes Ι-lOmg an oxide selected from copper oxide, nickel oxide, ferrous oxide, ferric oxide, triiron tetroxide, and chromium oxide.
2.如权利要求I所述的用于可见光催化还原水制氢的催化剂,其特征在于,所述氧化物为氧化铜。 2. I claim the visible light catalytic reduction catalyst for hydrogen production from water, wherein said oxide is copper oxide.
3.如权利要求2所述的用于可见光催化还原水制氢的催化剂,其特征在于,所述催化剂中的曙红Y、碳纳米管和氧化铜的质量比为O. 5 :1 :0. 06。 Visible claim for catalytic reduction catalyst for producing hydrogen according to the water 2, wherein the catalyst mass eosin Y, a carbon nanotube and copper oxide ratio of O. 5: 1: 0 06.
4.如权利要求I所述的用于可见光催化还原水制氢的催化剂,其特征在于,所述氧化物为氧化铁。 4. I claim the visible light catalytic reduction catalyst for hydrogen production from water, wherein said oxide is an iron oxide.
5. 一种制备如权利要求1-4中的任一项所述的用于可见光催化还原水制氢的催化剂的方法,其特征在于,首先制备碳纳米管-金属盐前驱体;将所述前驱体放入马弗炉中, 空气气氛下,200-400° C下煅烧数小时,得到碳纳米管-金属氧化物体系;将所述碳纳米管-金属氧化物体系放入曙红Y的水溶液中N2保护下浸泡,分离,得到所述的催化剂。 A preparation as claimed in any one of claims 1-4 for visible light catalytic process water into hydrogen reduction catalyst as claimed in claim, characterized in that, firstly preparing a carbon nanotube - metal salt precursor; the precursor placed in a muffle furnace under air atmosphere, 200-400 ° C for several hours calcination, the carbon nanotube - metal oxide systems; the carbon nanotube - metal oxide systems into eosin Y under the protection of N2 soaking solution, separated, to obtain the catalyst.
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