CN106076383A - A kind of simple and convenient process for preparing of nickel/class graphene carbon nitrogen compound composite catalyst - Google Patents
A kind of simple and convenient process for preparing of nickel/class graphene carbon nitrogen compound composite catalyst Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 4
- 229910021389 graphene Inorganic materials 0.000 title claims description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 229910001453 nickel ion Inorganic materials 0.000 abstract 1
- 238000007540 photo-reduction reaction Methods 0.000 abstract 1
- 239000003504 photosensitizing agent Substances 0.000 abstract 1
- 238000007872 degassing Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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Abstract
本发明的目的是针对目前环境污染及其能源危机等问题，创立简便方法制备一种镍/类石墨烯碳氮化合物复合催化剂，从而降低光催化剂成本、提高光催化分解水产氢速率。该复合催化剂的制备方法绿色环保，其原理是以类石墨烯碳氮化合物为光敏剂，使用光还原方法还原镍离子制备得到镍单质/类石墨烯碳氮化合物复合催化剂。本发明所制备的镍单质/类石墨烯碳氮化合物复合催化剂合成方法简便、光催化产氢速率高、稳定性好、价格低廉，应用于工业生产中可大幅度节约成本，且无毒环保，是一种有较大工业光催化产氢前景的新型催化材料。
The purpose of the present invention is to solve the current problems of environmental pollution and energy crisis, and create a simple method to prepare a nickel/graphene-like carbon-nitrogen compound catalyst, thereby reducing the cost of photocatalysts and increasing the hydrogen production rate of photocatalytic decomposition of water. The preparation method of the composite catalyst is green and environment-friendly, and its principle is to use the graphene-like carbon-nitrogen compound as a photosensitizer, and use a photoreduction method to reduce nickel ions to prepare a nickel simple substance/graphene-like carbon-nitrogen compound composite catalyst. The nickel simple substance/graphene-like carbon-nitrogen compound composite catalyst prepared by the present invention has a simple synthesis method, high photocatalytic hydrogen production rate, good stability, and low price. It can greatly save costs when applied to industrial production, and is non-toxic and environmentally friendly. It is a new type of catalytic material with great prospects for industrial photocatalytic hydrogen production.
Description
技术领域technical field
本发明提出一种金属镍单质/类石墨烯碳氮化合物复合催化剂的简便制备方法，属于材料科学技术领域和光催化制氢领域。The invention proposes a simple method for preparing a metal nickel element/graphene-like carbon-nitrogen compound composite catalyst, which belongs to the field of material science and technology and the field of photocatalytic hydrogen production.
背景技术Background technique
全球环境污染、能源危机日益严重，开发新型可持续能源备受世界各国的关注。其中氢气因其来源丰富、燃烧值高效、燃烧产物清洁无污染等优点，被认为是最理想的能源。分解水制氢是有可能实现大规模生产氢气的重要方法之一。而利用太阳能分解水产氢，将太阳能转换为存储于氢能源中的化学能，这就提供了一种获得氢气的廉价、便捷的方法。开发廉价高效的光催化剂是光催化分解水制氢的关键。Global environmental pollution and energy crisis are becoming more and more serious, and the development of new sustainable energy has attracted the attention of countries all over the world. Among them, hydrogen is considered to be the most ideal energy source because of its abundant sources, high combustion value, and clean and pollution-free combustion products. Hydrogen production by splitting water is one of the important methods to achieve large-scale production of hydrogen. Using solar energy to decompose water to produce hydrogen, and converting solar energy into chemical energy stored in hydrogen energy, provides a cheap and convenient way to obtain hydrogen. The development of cheap and efficient photocatalysts is the key to photocatalytic water splitting for hydrogen production.
类石墨烯碳氮化合物(又称g-C3N4)是一种无金属化合物，禁带宽度约为2.75eV，原料廉价、制备简便，具有良好的热稳定性和化学稳定性，从而具有广泛的研究及应用前景。镍元素广泛存在于自然界中，廉价易得。单纯的类石墨烯碳氮化合物由于光生载流子快速复合，导致其光催化产氢速率极低，将金属镍单质与类石墨烯碳氮化合物复合制备光催化剂可以抑制类石墨烯碳氮化合物光生载流子复合，从而大幅度提高光催化分解水制氢速率。Graphene-like carbonitride (also known as gC 3 N 4 ) is a metal-free compound with a bandgap of about 2.75eV. The raw material is cheap, easy to prepare, and has good thermal and chemical stability, so it has a wide range of applications. Research and application prospects. Nickel element widely exists in nature and is cheap and easy to get. Simple graphene-like carbonitrides have a very low photocatalytic hydrogen production rate due to the rapid recombination of photogenerated carriers. The photocatalyst prepared by combining metallic nickel with graphene-like carbonitrides can inhibit the photogenerated generation of graphene-like carbonitrides. The recombination of carriers can greatly increase the hydrogen production rate of photocatalytic water splitting.
本发明成功制备的金属镍单质/类石墨烯碳氮化合物复合催化剂，价格低廉，稳定性好，具有较高的光催化产氢速率，且尚无文献报道。The metal nickel simple substance/graphene-like carbon-nitrogen compound composite catalyst successfully prepared by the present invention has low price, good stability and high photocatalytic hydrogen production rate, and there is no literature report yet.
发明内容Contents of the invention
本发明的目的是针对目前环境污染及其能源危机等问题，创立简便方法制备一种镍单质/类石墨烯碳氮化合物复合催化剂，从而降低光催化剂成本、提高光催化分解水产氢速率。该复合催化剂的制备方法绿色环保，并且制备的复合催化剂具有较长寿命，48h后仍较高的催化活性。The purpose of the present invention is to solve the current problems of environmental pollution and energy crisis, and create a simple method to prepare a nickel element/graphene-like carbon-nitrogen compound composite catalyst, thereby reducing the cost of the photocatalyst and increasing the hydrogen production rate of photocatalytic decomposition of water. The preparation method of the composite catalyst is green and environment-friendly, and the prepared composite catalyst has a long service life and still has high catalytic activity after 48 hours.
本发明的技术方案，提出一种镍单质/类石墨烯碳氮化合物复合催化剂的简便制备方法，步骤为：The technical scheme of the present invention proposes a simple and convenient preparation method of nickel simple substance/graphene-like carbonitride compound catalyst, the steps are:
(1)取适量硫脲置于坩埚中，将坩埚置于马弗炉中550℃煅烧2h，待马弗炉降至室温取出坩埚，将黄色固体后、置于坩埚中，将坩埚置于马弗炉中500℃煅烧2h，待马弗炉降至室温取出黄白色粉末即为类石墨烯碳氮化合物(g-C3N4)；(1) Take an appropriate amount of thiourea and place it in a crucible, place the crucible in a muffle furnace for calcination at 550°C for 2 hours, take out the crucible after the muffle furnace has dropped to room temperature, put the yellow solid in the crucible, and place the crucible in the muffle furnace Calcinate in a muffle furnace at 500°C for 2 hours, and take out the yellow-white powder after the muffle furnace cools down to room temperature, which is graphene-like carbonitride (gC 3 N 4 );
(2)取一定量的类石墨烯碳氮化合物(g-C3N4)加入25mL单口圆底烧瓶，加入一定量次磷酸钠(分子式NaH2PO2)和氯化镍的混合水溶液，加入适量水和三乙醇胺，混合均匀后通入氮气30-40min以除去反应体系中氧气，然后置于氙灯下光照，光照时保持均匀搅拌；(2) Take a certain amount of graphene-like carbon nitrogen compound (gC 3 N 4 ) and add it to a 25mL single-necked round bottom flask, add a certain amount of sodium hypophosphite (molecular formula NaH 2 PO 2 ) and a mixed aqueous solution of nickel chloride, add an appropriate amount of water and triethanolamine, after mixing evenly, pass nitrogen gas for 30-40 minutes to remove oxygen in the reaction system, then place it under a xenon lamp for light, and keep stirring evenly during light;
(3)反应结束后，使用离心分离将固体分离，去离子水离心洗涤5-8次，乙醇洗涤1-3次，将所得固体物质干燥，所得黑色固体物质即为产品镍单质/类石墨烯碳氮化合物复合催化剂。(3) After the reaction is over, use centrifugation to separate the solid, centrifugally wash 5-8 times with deionized water, wash with ethanol 1-3 times, dry the obtained solid substance, and the obtained black solid substance is the product nickel element/graphene Carbon nitrogen compound catalyst.
本发明的有益效果：本发明使用简便的光沉积方法可以快速制得金属镍单质/类石墨烯碳氮化合物复合催化剂，所得金属纳米粒子均匀分散在类石墨烯碳氮化合物表面，且其粒径大小约为30-90nm，原料廉价、方法简便，降低了催化剂制备的成本；所制备催化剂具有磁性，用于液-固相反应，便于反应后分离、多次循环利用，降低了催化剂使用成本；采用镍单质作为光催化反应的助催化剂，大幅度提高催化效率，相比较其他同类型过渡金属助催化剂，具有更高的光催化活性。本发明所制备的镍单质/类石墨烯碳氮化合物复合催化剂，可用于光催化分解水产氢反应，价格低廉，且产氢速率较高。Beneficial effects of the present invention: the present invention can quickly prepare metallic nickel simple substance/graphene-like carbonitride composite catalyst by using a simple photodeposition method, and the obtained metal nanoparticles are uniformly dispersed on the surface of graphene-like carbonitride, and the particle size The size is about 30-90nm, the raw material is cheap, and the method is simple, which reduces the cost of catalyst preparation; the prepared catalyst is magnetic and used for liquid-solid phase reactions, which is convenient for separation after reaction and repeated recycling, reducing the cost of catalyst use; The use of simple nickel as a co-catalyst for photocatalytic reactions greatly improves the catalytic efficiency. Compared with other transition metal co-catalysts of the same type, it has higher photocatalytic activity. The nickel simple substance/graphene-like carbon-nitrogen compound composite catalyst prepared by the invention can be used for the hydrogen production reaction of photocatalytic decomposition of water, and has low price and high hydrogen production rate.
附图说明Description of drawings
图1是实施例1所得类石墨烯碳氮化合物和镍单质/类石墨烯碳氮化合物复合催化剂的XRD图谱。Fig. 1 is the XRD spectrum of the obtained graphene-like carbonitride compound and nickel simple substance/graphene-like carbonitride compound catalyst obtained in Example 1.
图2是实施例1所得镍单质/类石墨烯碳氮化合物复合催化剂的透射电镜图片及其高分辨透射电镜图片。Fig. 2 is the transmission electron microscope picture and its high-resolution transmission electron microscope picture of nickel simple substance/graphene-like carbonitride compound catalyst obtained in embodiment 1.
图3是实施例1所得镍单质/类石墨烯碳氮化合物复合催化剂的透射电镜能量色散X射线光谱。Fig. 3 is the transmission electron microscopy energy dispersive X-ray spectrum of the nickel simple substance/graphene-like carbonitride composite catalyst obtained in Example 1.
图4是实施例1所得镍单质/类石墨烯碳氮化合物复合催化剂光催化产氢测试图。Fig. 4 is the photocatalytic hydrogen production test diagram of nickel simple substance/graphene-like carbonitride composite catalyst obtained in Example 1.
具体实施方式detailed description
下面结合一些实例和附图对本发明做进一步说明，但本发明的权利范围不仅限于实施例的范围。The present invention will be further described below in conjunction with some examples and accompanying drawings, but the scope of rights of the present invention is not limited to the scope of the embodiments.
实施例1Example 1
(1)取20g硫脲置于4个坩埚中，将坩埚置于马弗炉中以2度每分的升温速率升至550℃，煅烧两小时，待降至室温取出坩埚，将固体研磨成粉末，将盛有固体粉末的坩埚置于马弗炉，以2度每分升温速率升至500℃，煅烧两小时，待降至室温取出黄白色固体粉末获得类石墨烯碳氮化合物；(1) Take 20g of thiourea and place it in 4 crucibles, place the crucibles in a muffle furnace and raise the temperature to 550°C at a rate of 2 degrees per minute, calcinate for two hours, take out the crucibles when the temperature drops to room temperature, and grind the solid into Powder, put the crucible containing the solid powder in a muffle furnace, raise the temperature to 500°C at a rate of 2°C per minute, calcinate for two hours, and take out the yellow-white solid powder after cooling down to room temperature to obtain graphene-like carbon nitrogen compounds;
(2)取10mg石墨烯碳氮化合物置于25mL单口烧瓶中，随后加入3mL三乙醇胺，0.3mL硫化镍水溶液(0.1mol/L)，2.1mL次磷酸钠(分子式NaH2PO2)水溶液(0.1mol/L)，4.6mL水，超声分散处理30s，然后使用氮气脱气40min除去反应体系中氧气；(2) Take 10 mg of graphene carbon nitrogen compound and place it in a 25 mL single-necked flask, then add 3 mL of triethanolamine, 0.3 mL of nickel sulfide aqueous solution (0.1 mol/L), 2.1 mL of sodium hypophosphite (molecular formula NaH 2 PO 2 ) aqueous solution (0.1 mol/L), 4.6mL water, ultrasonic dispersion treatment for 30s, and then use nitrogen degassing for 40min to remove oxygen in the reaction system;
(3)待脱气完成后，将圆底烧瓶置于300W氙光灯下照射30min后，将所得固体离心分离，去离子水洗涤5次，乙醇洗涤2次，将固体80℃真空干燥10h，所得黑色物质即为镍单质/类石墨烯碳氮化合物复合催化剂。所制备镍单质/类石墨烯碳氮化合物复合催化剂中镍的质量百分含量为7.4％。(3) After the degassing is completed, place the round-bottomed flask under a 300W xenon lamp for 30 minutes, then centrifuge the obtained solid, wash it with deionized water 5 times, wash it with ethanol twice, and vacuum dry the solid at 80°C for 10 hours. The obtained black substance is nickel simple substance/graphene-like carbon-nitrogen compound composite catalyst. The mass percent content of nickel in the prepared nickel simple substance/graphene-like carbonitride composite catalyst is 7.4%.
将制备的光催化剂进行X射线衍射光谱(图1所示)，透射电镜(图2a所示)，高分辨透射电镜(图2b所示)及其能量色散X射线光谱(EDX)(图3所示)。The prepared photocatalyst was subjected to X-ray diffraction spectrum (shown in Figure 1), transmission electron microscope (shown in Figure 2a), high-resolution transmission electron microscope (shown in Figure 2b) and its energy dispersive X-ray spectrum (EDX) (shown in Figure 3 Show).
实施例2Example 2
(1)实施例1中类石墨烯碳氮化合物取10mg置于25mL圆底烧瓶中，随后加入3mL三乙醇胺，0.2mL硫化镍水溶液(0.1mol/L)，1.4mL次磷酸钠(分子式NaH2PO2)水溶液(0.1mol/L)，5.4mL水，超声分散处理30s，然后使用氮气脱气40min除去反应体系中氧气；(1) Graphene-like carbonitride in embodiment 1 gets 10mg and is placed in 25mL round bottom flask, then adds 3mL triethanolamine, 0.2mL nickel sulfide aqueous solution (0.1mol/L), 1.4mL sodium hypophosphite (molecular formula NaH 2 PO 2 ) aqueous solution (0.1mol/L), 5.4mL water, ultrasonic dispersion treatment for 30s, and then use nitrogen degassing for 40min to remove oxygen in the reaction system;
(2)待脱气完成后，将圆底烧瓶置于300W氙光灯下照射30min后，将所得固体离心分离，去离子水洗涤5次，乙醇洗涤2次，将固体80℃真空干燥10h，所得黑色物质即为镍单质/类石墨烯碳氮化合物复合催化剂。所制备的镍单质/类石墨烯碳氮化合物复合催化剂中镍的质量百分含量为3.8％。(2) After the degassing is completed, place the round-bottomed flask under a 300W xenon lamp for 30 minutes, then centrifuge the obtained solid, wash it with deionized water 5 times, wash it with ethanol twice, and dry the solid at 80°C for 10 hours under vacuum. The obtained black substance is nickel simple substance/graphene-like carbon-nitrogen compound composite catalyst. The mass percent content of nickel in the prepared nickel simple substance/graphene-like carbonitride compound catalyst is 3.8%.
实施例3Example 3
(1)实施例1中类石墨烯碳氮化合物取10mg置于25mL圆底烧瓶中，随后加入3mL三乙醇胺，0.4mL硫化镍水溶液(0.1mol/L)，2.8mL次磷酸钠(分子式NaH2PO2)水溶液(0.1mol/L)，3.8mL水，超声分散处理30s，然后使用氮气脱气40min除去反应体系中氧气；(1) 10 mg of graphene-like carbonitrides in embodiment 1 is placed in a 25mL round-bottomed flask, then 3mL of triethanolamine is added, 0.4mL of nickel sulfide aqueous solution (0.1mol/L), 2.8mL of sodium hypophosphite (molecular formula NaH 2 PO 2 ) aqueous solution (0.1mol/L), 3.8mL water, ultrasonic dispersion treatment for 30s, and then use nitrogen degassing for 40min to remove oxygen in the reaction system;
(2)待脱气完成后，将圆底烧瓶置于300W氙光灯下照射30min后，将所得固体离心分离，去离子水洗涤5次，乙醇洗涤2次，将固体80℃真空干燥10h，所得黑色物质即为镍单质/类石墨烯碳氮化合物复合催化剂。所制备的镍单质/类石墨烯碳氮化合物复合催化剂中镍的质量百分含量为12.2％。(2) After the degassing is completed, place the round-bottomed flask under a 300W xenon lamp for 30 minutes, then centrifuge the obtained solid, wash it with deionized water 5 times, wash it with ethanol twice, and dry the solid at 80°C for 10 hours under vacuum. The obtained black substance is nickel simple substance/graphene-like carbon-nitrogen compound composite catalyst. The mass percent content of nickel in the prepared nickel simple substance/graphene-like carbonitride compound catalyst is 12.2%.
实施例4Example 4
将实施例1中类石墨烯碳氮化合物取10mg置于25mL圆底烧瓶中，随后加入3mL三乙醇胺，7mL水。超声处理30s，使用氮气脱气40min排除体系中氧气，将圆底烧瓶置于太阳光模拟器下光照，反应结束后，用热导-气相色谱检测反应中生成的氢气，反应9h后其产氢速率为10.5μmol g-1h-1。10 mg of the graphene-like carbonitride in Example 1 was placed in a 25 mL round bottom flask, and then 3 mL of triethanolamine and 7 mL of water were added. Ultrasonic treatment for 30s, use nitrogen degassing for 40min to remove oxygen in the system, place the round bottom flask under a solar simulator for light, after the reaction, use thermal conductivity-gas chromatography to detect the hydrogen generated in the reaction, and react for 9h to produce hydrogen The rate is 10.5 μmol g -1 h -1 .
实施例5Example 5
将实施例1中镍单质/类石墨烯碳氮化合物复合催化剂取10mg置于25mL圆底烧瓶中，随后加入3mL三乙醇胺，7mL水。超声处理30s，使用氮气脱气40min排除体系中氧气，将圆底烧瓶置于太阳光模拟器下光照，反应结束后，用热导-气相色谱检测反应中生成的氢气，反应9h后其产氢速率为4318μmol g-1h-1，比单纯的类石墨烯碳氮化合物产氢速率提高410倍。Put 10 mg of nickel element/graphene-like carbonitride composite catalyst in Example 1 into a 25 mL round bottom flask, then add 3 mL of triethanolamine and 7 mL of water. Ultrasonic treatment for 30s, use nitrogen degassing for 40min to remove oxygen in the system, place the round bottom flask under a solar simulator for light, after the reaction, use thermal conductivity-gas chromatography to detect the hydrogen generated in the reaction, and react for 9h to produce hydrogen The rate is 4318μmol g -1 h -1 , which is 410 times higher than that of simple graphene-like carbon nitrogen compounds.
实施例6Example 6
将实施例1中镍单质/类石墨烯碳氮化合物复合催化剂取2mg置于25mL圆底烧瓶中，随后加入3mL三乙醇胺、7mL水。超声处理30s，使用氮气脱气40min排除体系中氧气，将圆底烧瓶置于太阳光模拟器下光照。每隔3h用热导-气相色谱检测反应中生成的氢气，每隔12h进行一次脱气排除体系中氢气，待反应48h后催化剂活性仍无明显降低(图4所示)。Put 2 mg of nickel element/graphene-like carbonitride composite catalyst in Example 1 into a 25 mL round bottom flask, then add 3 mL of triethanolamine and 7 mL of water. Sonicate for 30 s, use nitrogen degassing for 40 min to remove oxygen in the system, and place the round bottom flask under a solar simulator for light. The hydrogen generated in the reaction was detected by thermal conductivity-gas chromatography every 3 hours, and the hydrogen in the system was degassed every 12 hours. After 48 hours of reaction, the catalyst activity still did not decrease significantly (as shown in Figure 4).
由上述各实施例及图4可看出，本发明所制备的镍单质/类石墨烯碳氮化合物复合催化剂合成方法简便、光催化产氢速率高、稳定性好、价格低廉，应用于工业生产中可大幅度节约成本，且无毒环保，是一种有较大工业光催化产氢前景的新型催化材料。As can be seen from the above embodiments and Figure 4, the nickel simple substance/graphene-like carbonitride composite catalyst prepared by the present invention has a simple synthesis method, high photocatalytic hydrogen production rate, good stability, and low price, and is suitable for industrial production It can greatly save costs, and is non-toxic and environmentally friendly. It is a new type of catalytic material with great prospects for industrial photocatalytic hydrogen production.
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