CN109261190A - 一种Ni-Mo/g-C3N4复合光催化剂及其制备和应用 - Google Patents
一种Ni-Mo/g-C3N4复合光催化剂及其制备和应用 Download PDFInfo
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- 229910003296 Ni-Mo Inorganic materials 0.000 title claims abstract description 58
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 89
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- UGDAWAQEKLURQI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;hydrate Chemical compound O.OCCOCCO UGDAWAQEKLURQI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000016768 molybdenum Nutrition 0.000 claims 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
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- 229910021641 deionized water Inorganic materials 0.000 description 4
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- 230000000694 effects Effects 0.000 description 3
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种Ni‑Mo/g‑C3N4复合光催化剂及其制备和应用,催化剂是由Ni‑Mo合金纳米颗粒和g‑C3N4材料构筑而成的复合物;该催化剂的制备方法是以g‑C3N4为基体,通过一步还原法还原g‑C3N4与Ni‑Mo合金的前驱体制备得到;该复合光催化剂可有效降低光生电子与空穴的复合,提高光生电子与空穴的利用率,延长光催化剂的使用寿命,可用于光分解水制氢反应并具有较高的效率;其制备方法和所需设备简单,成本低,制备周期短且易于大规模生产。
Description
技术领域
本发明属于可见光催化剂及其制备和应用领域,特别涉及一种Ni-Mo/g-C3N4复合光催化剂及其制备和应用。
背景技术
氢能是公认的清洁能源,作为低碳和零碳能源正在脱颖而出。21世纪,我国和美国、日本、加拿大、欧盟等都制定了氢能发展规划,并且目前我国已在氢能领域取得了多方面的进展,在不久的将来有望成为氢能技术和应用领先的国家之一。世界各国正在研究如何能大量而廉价的生产氢。利用太阳能来分解水是一个主要研究方向,在光的作用下将水分解成氢气和氧气,关键在于找到一种合适的催化剂。近年来,一种新型的、可见光下响应的非金属材料g-C3N4,由于禁带宽度(约2.7eV)较窄、化学稳定性好、制备方法简便等优点受到广泛的关注。但g-C3N4在光照下所产生的光生电子与空穴极易复合,导致其光催化的效果并不理想。为了抑制光生电子-空穴对的复合,可以将一些贵金属沉积在g-C3N4的表面作为助催化剂,提升其光生电子的输送效率,并抑制光生电子和空穴的复合,从而提高光催化效率。已见报道的贵金属主要包括Pt、Ag、Ir、Au、Ru、Pd、Rh等,其中有关Pt的报道最多,效果也最好。
然而,Pt等贵金属在地壳中含量稀少,价格昂贵,严重制约了Pt等贵金属在光催化领域中的应用。因此,开发廉价的地壳中富含的元素组成的非贵金属材料作为半导体光催化剂的共催化剂就显得尤为重要。我们注意到,在光电催化领域中已经被广泛研究的非贵金属Ni-Mo合金可能是一种有望能在光催化领域中代替贵金属Pt的一种理想的非贵金属共催化剂。然而现有技术只能将Ni-Mo合金沉积到光电催化剂负载的导电基底上制备成合适的电极进行应用,这并不能满足其在粉末光催化体系中的应用。
发明内容
本发明所要解决的技术问题是提供一种Ni-Mo/g-C3N4复合光催化剂及其制备和应用,克服现有技术中采用贵金属沉积在g-C3N4的表面作为助催化剂成本高、不利于推广的技术缺陷,该制备方法简单,工艺参数容易控制,易于大规模化生产,得到的复合催化剂成本低,且具有较高的可见光分解水产氢的效率以及稳定性。
本发明的一种Ni-Mo/g-C3N4复合光催化剂的制备方法,包括:
(1)将镍源和钼源加入去水中至全部溶解,然后加入氨水溶液,再加入二甘醇,搅拌,加热,离心水洗,干燥,得到Ni-Mo合金的前驱体;
(2)将g-C3N4与步骤(1)的Ni-Mo合金的前驱体混合,在还原气氛下煅烧,得到Ni-Mo/g-C3N4复合光催化剂。
上述制备方法的优选方式如下:
所述镍源为六水合硝酸镍;钼源为七钼酸铵。
所述步骤(1)中镍源与钼源的质量比为1:9~9:1;加入的氨水溶液、二甘醇和水的体积比为1:45:5~5:45:5。
所述步骤(1)中加热温度为100-180℃;干燥温度为60-120℃。
所述步骤(2)中g-C3N4与Ni-Mo合金的前驱体的质量比为1:1~9:1。
所述步骤(2)中还原气氛下煅烧为:氩氢混合气为还原气氛,煅烧温度为200~500℃,升温速率为4~10℃/min。
所述煅烧为:以4~10℃/min的升温速率先200-250℃保温20-35min,再升至400-500℃保温0.5-1h。
本发明提高一种所述方法制备的Ni-Mo/g-C3N4复合光催化剂。
所述催化剂为Ni-Mo纳米颗粒和g-C3N4材料构筑而成的复合物,其中Ni-Mo合金的负载量为1wt%-30wt%。
本发明的一种所述Ni-Mo/g-C3N4复合光催化剂的应用。
有益效果
(1)本发明工艺和设备简单,工艺参数容易控制,成本低廉,易于大规模生产;
(2)本发明复合光催化剂可有效降低光生电子与空穴的复合,提高光生电子与空穴的利用率,光催化剂的光催化性能较好,可用于光分解水制氢反应并具有较高的效率;其制备方法和所需设备简单,成本低,制备周期短且易于大规模生产;
(3)本发明通过一步还原煅烧法制备了一种Ni-Mo/g-C3N4复合光催化剂,成本低廉;Ni-Mo合金纳米颗粒可均匀分散于g-C3N4表面,并能与g-C3N4材料形成较好的接触,有利于光生电子快速向Ni-Mo合金转移,有效提高材料的光生电子与空穴的分离效率,提升其光催化性能,得到的Ni-Mo/g-C3N4复合光催化剂材料在可见光下具有较好的光催化产氢性能,其性能是纯g-C3N4的7.5倍左右,并且具有较好的光催化循环稳定性;
(4)本发明制备得到的Ni-Mo/g-C3N4复合材料在可见光下的产氢性能基本达到了贵金属Pt负载的g-C3N4光催化剂的性能,因此Ni-Mo合金是能在光催化领域中代替贵金属Pt的一种理想的非贵金属共催化剂;
(5)本发明制备得到的Ni-Mo/g-C3N4复合材料结晶性好,颗粒细小且分布均匀,导电性良好,具有较好的光催化性能,在光催化、废水处理等领域有应用价值。
附图说明
图1是实施例1制备的Ni-Mo/g-C3N4复合光催化剂与纯g-C3N4的XRD图;
图2是实施例1制备的Ni-Mo/g-C3N4复合光催化剂与纯g-C3N4的紫外可见漫反射光谱;
图3是实施例1制备的Ni-Mo/g-C3N4复合光催化剂与纯g-C3N4的光催化产氢曲线;
图4是实施例1制备的Ni-Mo/g-C3N4复合光催化剂的循环光催化产氢曲线;
图5是实施例3制备的Ni-Mo/g-C3N4复合光催化剂的TEM图像;
图6是实施例1和对比例1中的光催化剂的光催化产氢率的对比图。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
(1)将3g六水合硝酸镍和2.76g七钼酸铵加入5mL的去离子水中搅拌5min,然后在搅拌状态下加入2ml 28%的氨水溶液,随后加入45ml二甘醇,继续搅拌5min,将上述混合溶液置于油浴锅中加热至130℃后取出自然冷却30s,然后离心水洗三次并于60℃下干燥,得到Ni-Mo合金的前驱体。
(2)将0.18gg-C3N4与0.02g步骤(1)中的Ni-Mo合金的前驱体置于研钵中并充研磨,置于管式炉中,在氩氢混合气下,以5℃/min的升温速率先200℃保温30min再升至450摄氏度保温1h,随后自然冷却到室温后便得到Ni-Mo/g-C3N4复合光催化剂。
将该Ni-Mo/g-C3N4复合光催化剂和纯g-C3N4进行光催化产氢,光催化产氢的条件为:20mg催化剂置于含有10vol%三乙醇胺的水溶液中,用带有≧420nm可见光滤光片的300W氙灯为可见光光源,在可见光光源的连续照射下每一小时取样一次并用气相色谱检测氢气的产量。
图1表明:本实施例得到的Ni-Mo/g-C3N4复合光催化剂材料在2θ=13°,27.5°出现了g-C3N4的特征峰,在2θ=44.5°,51.9°出现了Ni-Mo合金的特征峰,说明本实施例最终制备的物质为g-C3N4与Ni-Mo合金的复合物。
图2表明:本实施例得到的Ni-Mo/g-C3N4复合光催化剂材料相比于纯g-C3N4有更好的吸光性能。
图3表明:本实施例得到的Ni-Mo/g-C3N4复合光催化剂材料在可见光下具有较好的光催化产氢性能,其性能是纯g-C3N4的7.5倍左右。
图4表明:本实施例得到的Ni-Mo/g-C3N4复合光催化剂材料经过5次光催化产氢循环试验后其性能没有明显的下降,因此此复合光催化剂材料具有较好的光催化循环稳定性。
实施例2
(1)将3g六水合硝酸镍和1.2g七钼酸铵加入5mL的去离子水中搅拌5min,然后在搅拌状态下加入3ml28%的氨水溶液,随后加入45ml二甘醇,继续搅拌5min,将上述混合溶液置于油浴锅中加热至140℃后取出自然冷却30s,然后离心水洗三次并于120℃下干燥,得到Ni-Mo合金的前驱体。
(2)将0.19gg-C3N4与0.01g步骤(1)中的Ni-Mo合金的前驱体置于研钵中并充研磨,置于管式炉中,在氩氢混合气下,以4℃/min的升温速率先200℃保温30min再升至400摄氏度保温1h,随后自然冷却到室温后便得到Ni-Mo/g-C3N4复合光催化剂。
实施例3
(1)将1.5g六水合硝酸镍和0.92g七钼酸铵加入5mL的去离子水中搅拌5min,然后在搅拌状态下加入3ml28%的氨水溶液,随后加入45ml二甘醇,继续搅拌5min,将上述混合溶液置于油浴锅中加热至120℃后取出自然冷却30s,然后离心水洗三次并于100℃下干燥,得到Ni-Mo合金的前驱体。
(2)将0.13gg-C3N4与0.7g步骤(1)中的Ni-Mo合金的前驱体置于研钵中并充研磨,置于管式炉中,在氩氢混合气下,以10℃/min的升温速率先200℃保温30min再升至450摄氏度保温1h,随后自然冷却到室温后便得到Ni-Mo/g-C3N4复合光催化剂。
从图5中可以看出Ni-Mo纳米颗粒附着在g-C3N4片层的表面,有利于g-C3N4的光生电子的传导,但因本实施例中Ni-Mo合金的含量过高导致其在g-C3N4的表面分布的并不均匀且发生了团聚现象。
实施例4
(1)将0.9g六水合硝酸镍和0.1g七钼酸铵加入5mL的去离子水中搅拌5min,然后在搅拌状态下加入1ml28%的氨水溶液,随后加入45ml二甘醇,继续搅拌5min,将上述混合溶液置于油浴锅中加热至180℃后取出自然冷却30s,然后离心水洗三次并于120℃下干燥,得到Ni-Mo合金的前驱体。
(2)将0.09gg-C3N4与0.01g步骤(1)中的Ni-Mo合金的前驱体置于研钵中并充研磨,置于管式炉中,在氩氢混合气下,以10℃/min的升温速率先200℃保温30min再升至500摄氏度保温1h,随后自然冷却到室温后便得到Ni-Mo/g-C3N4复合光催化剂。
对比例1
贵金属Pt负载的g-C3N4光催化剂的光催化产氢性能的测试。光催化产氢的条件为:20mg g-C3N4催化剂置于含有10vol%三乙醇胺和1.1mg氯铂酸的水溶液中,用带有≧420nm可见光滤光片的300W氙灯为可见光光源,在可见光光源的连续照射下每一小时取样一次并用气相色谱检测氢气的产量。
图6表明:实施例1中制备得到的Ni-Mo/g-C3N4复合光催化剂在可见光下的产氢性能可达到贵金属Pt负载的g-C3N4催化剂的性能的84%,非贵金属助催化剂Ni-Mo合金可替代金属Pt在光催化领域中应用。
Claims (8)
1.一种Ni-Mo/g-C3N4复合光催化剂的制备方法,包括:
(1)将镍源和钼源加入去水中至全部溶解,然后加入氨水溶液,再加入二甘醇,搅拌,加热,离心水洗,干燥,得到Ni-Mo合金的前驱体;
(2)将g-C3N4与步骤(1)的Ni-Mo合金的前驱体混合,在还原气氛下煅烧,得到Ni-Mo/g-C3N4复合光催化剂。
2.根据权利要求1所述制备方法,其特征在于,所述镍源为六水合硝酸镍;钼源为七钼酸铵。
3.根据权利要求1所述制备方法,其特征在于,所述步骤(1)中镍源与钼源的质量比为1:9~9:1;加入的氨水溶液、二甘醇和水的体积比为1:45:5~5:45:5。
4.根据权利要求1所述制备方法,其特征在于,所述步骤(1)中加热温度为100-180℃;干燥温度为60-120℃。
5.根据权利要求1所述制备方法,其特征在于,所述步骤(2)中g-C3N4与Ni-Mo合金的前驱体的质量比为1:1~9:1。
6.根据权利要求1所述制备方法,其特征在于,所述步骤(2)中还原气氛下煅烧为:氩氢混合气为还原气氛,煅烧温度为200~500℃,升温速率为4~10℃/min。
7.一种权利要求1所述方法制备的Ni-Mo/g-C3N4复合光催化剂。
8.一种权利要求1所述Ni-Mo/g-C3N4复合光催化剂的应用。
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