CN110479335B - 一种铜原位掺杂的碳化钼碳复合材料及其制备方法 - Google Patents
一种铜原位掺杂的碳化钼碳复合材料及其制备方法 Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
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- 238000000034 method Methods 0.000 claims abstract description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 19
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- KHSTZMGCKHBFJX-UHFFFAOYSA-N 3-(dibutylamino)phenol Chemical compound CCCCN(CCCC)C1=CC=CC(O)=C1 KHSTZMGCKHBFJX-UHFFFAOYSA-N 0.000 claims description 3
- -1 molybdate ions Chemical class 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- DSEQJUPGRWESKP-UHFFFAOYSA-N n-(2-hydroxy-5-methylphenyl)acetamide Chemical group CC(=O)NC1=CC(C)=CC=C1O DSEQJUPGRWESKP-UHFFFAOYSA-N 0.000 claims description 2
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002243 precursor Substances 0.000 abstract description 12
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
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Abstract
本发明公开了一种铜原位掺杂的碳化钼碳复合材料及其制备方法,属于无机纳米材料制备领域。本发明的铜原位掺杂的碳化钼碳复合材料的制备方法,利用铜盐、钼酸盐为原料,通过超声制备了钼酸铜前驱体,并通过氨基苯酚衍生物与钼酸铜的配位作用对其结构进行调控,同时对其表面进行包覆,煅烧后能够将前驱体原位转化为铜原位掺杂的碳化钼碳复合材料;该制备方法工艺简单、能耗低、对环境无污染,适合工业化规模生产,不同于现有技术中从外向内的掺杂方式,本发明的制备方法利用钼酸铜的自转换反应,将导电性较好的金属铜原位掺杂到碳化钼中,克服了现有技术掺杂不均匀、掺杂工艺较复杂的问题。
Description
技术领域
本发明属于无机纳米材料制备领域,尤其是一种铜原位掺杂的碳化钼碳复合材料及其制备方法。
背景技术
碳化钼具有类似贵金属的电子结构和优良的催化性能,是目前新型无机催化材料研究领域的一个热点。其对于烃类脱氢、烃类脱氮、氢解和异构化反应的催化活性、费托合成以及甲烷重整等,可与贵金属铂、铱等相媲美,被称为“类铂催化剂”。但是纯的碳化钼易于团聚,使得其电化学活性位点无法得到充分暴露,严重影响了其催化特性。因此,将碳化钼与稳定性优异的碳纳米材料进行有效复合具有重要意义。
中国发明专利201811551171.8采用水热法及后期煅烧制备了一种碳化钼碳复合材料,发现其作为电极材料具有优异的电化学性能。中国发明专利201811487558.1采用溶胶-凝胶法,通过添加模板剂及后期煅烧制备了一种三维介孔碳负载碳化钼。中国发明专利201811019898.1则首先采用改进Hummers法制备水溶性氧化石墨烯,然后与钼盐混合并进行煅烧处理,制备了一种氮掺杂碳化钼/石墨烯复合材料,并测试了其相关的电化学性能。为进一步提高碳化钼的电化学性能,人们采用金属单质或离子对其进行掺杂改性。如中国发明专利201910088084.1采用水热法将镍单质掺杂到碳化钼纳米片中,提高了其电催化性能。
发明内容
本发明的目的在于克服上述现有技术的缺点,提供一种铜原位掺杂的碳化钼碳复合材料及其制备方法。
为达到上述目的,本发明采用以下技术方案予以实现:
一种铜原位掺杂的碳化钼碳复合材料的制备方法,包括以下步骤:
1)配制铜盐水溶液和钼酸盐水溶液;其中,所述铜盐水溶液中铜离子的浓度为0.1-0.4mol/L,所述钼酸盐水溶液中钼酸根离子的浓度为0.05-0.1mol/L;
2)将所述钼酸盐水溶液按体积比为1:(0.5-1)滴加到40-60℃的铜盐水溶液中,得到的混合液,将混合液在50-70W功率下超声10-30min进行反应,反应结束后进行过滤、清洗、干燥得到产物A;
3)将产物A分散在氨基苯酚衍生物水溶液中,得到反应液,将反应液在室温下搅拌4-10h进行反应,反应结束后经过滤、清洗、干燥后得到产物B;
其中,氨基苯酚衍生物水溶液的浓度为0.01~0.04mol/L,每100mL氨基苯酚衍生物水溶液中加入20mg产物A;
4)将产物B在惰性气体的气氛下、800-900℃煅烧2h,得到铜原位掺杂的碳化钼碳复合材料。
进一步的,步骤1)中铜盐为硝酸铜或醋酸铜。
进一步的,步骤1)中钼酸盐为钼酸钠或钼酸铵。
进一步的,步骤3)中氨基苯酚衍生物为2-羟基-5-甲基乙酰苯胺、3-(二丁氨基)苯酚或4-(2-氨基乙基)-1,2-苯二酚。
上述制备方法制备得到的铜原位掺杂的碳化钼碳复合材料。
上述制备方法制备得到的铜原位掺杂的碳化钼碳复合材料在电解水析氢催化剂上的应用。
与现有技术相比,本发明具有以下有益效果:
本发明的铜原位掺杂的碳化钼碳复合材料的制备方法,利用铜盐、钼酸盐为原料,通过超声制备了钼酸铜前驱体,并通过氨基苯酚衍生物与钼酸铜的配位作用对其结构进行调控,同时对其表面进行包覆,煅烧后能够将前驱体原位转化为铜原位掺杂的碳化钼碳复合材料;该制备方法工艺简单、能耗低、对环境无污染,适合工业化规模生产,不同于现有技术中从外向内的掺杂方式,本发明的制备方法利用钼酸铜的自转换反应,将导电性较好的金属铜原位掺杂到碳化钼中,克服了现有技术掺杂不均匀、掺杂工艺较复杂的问题。
本发明的铜原位掺杂的碳化钼碳复合材料,金属铜原位掺杂到碳化钼中,并在其表面进行了均匀的碳包覆,铜碳化钼碳复合材料形貌规整、纯度与结晶度较好,金属铜掺杂均匀,在催化、电化学等领域具有较强的应用前景。
附图说明
图1为本发明的实施例1的铜原位掺杂的碳化钼碳复合材料的SEM图;
图2为本发明的实施例1的铜原位掺杂的碳化钼碳复合材料XRD图;
图3为本发明的实施例1铜原位掺杂的碳化钼碳复合材料极化曲线。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分的实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本发明保护的范围。
需要说明的是,本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象,而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换,以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外,术语“包括”和“具有”以及他们的任何变形,意图在于覆盖不排他的包含,例如,包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元,而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
下面结合附图对本发明做进一步详细描述:
实施例1
1)分别配制浓度为0.1mol/L的硝酸铜和0.05mol/L的钼酸钠水溶液;
2)将钼酸钠水溶液按照1:0.5的体积比滴加到50℃的硝酸铜水溶液中,接着50W超声处理10min,清洗干燥后得到钼酸铜前驱体,记为产物A;
3)将20mg产物A超声分散于100mL浓度为0.01mol/L的2-羟基-5-甲基乙酰苯胺水溶液中,得到反应液,室温下搅拌4h,反应完成后经过滤、清洗、干燥后得到产物B;
4)将产物B在氩气气氛下800℃煅烧2h,得到铜碳化钼碳复合材料。
参见图1,图1为本发明的实施例1的铜原位掺杂的碳化钼碳复合材料的SEM图;从图中可见所制备的产品主要呈球状形貌,直径为60-80nm。
参见图2,图2为本发明的实施例1的铜原位掺杂的碳化钼碳复合材料XRD图;产品测试的2θ范围为5°-70°,产品的XRD衍射峰比较尖锐,铜原位掺杂的衍射峰比较明显,并未出现其它的杂峰,说明制备的产品纯度与结晶度较高。
参见图3,图3为本发明的实施例1铜原位掺杂的碳化钼碳复合材料极化曲线,以制备的铜原位掺杂的碳化钼碳复合材料作为催化剂活性物质,全氟磺酸-聚四氟乙烯共聚物(Nafion)为粘结剂,在玻碳电极上组装为工作电极,0.5mol/L的硫酸溶液为电解液,从图中可以看出该样品在电流密度为10mA/cm2时,电极析氢反应的过电位为364mV,说明该结构的铜碳化钼碳复合材料具有较好的电催化性能。
实施例2
1)分别配制浓度为0.4mol/L的醋酸铜水溶液和0.1mol/L的钼酸铵水溶液;
2)将钼酸铵水溶液按照1:1的体积比滴加到40℃的醋酸铜水溶液中,接着70W超声处理30min,清洗干燥后得到钼酸铜前驱体,记为产物A;
3)将30mg产物A超声分散于150mL浓度为0.02mol/L的2-羟基-5-甲基乙酰苯胺水溶液中,得到反应液,室温下搅拌10h,反应完成后经过滤、清洗、干燥后得到产物B;
4)将产物B在氮气气氛下、900℃煅烧2h,得到铜碳化钼碳复合材料。
实施例3
1)配制浓度为0.3mol/L的硝酸铜水溶液和0.07mol/L的钼酸钠水溶液;
2)将钼酸钠水溶液按照1:0.7的体积比滴加到60℃的硝酸铜水溶液中,接着60W超声处理20min,清洗干燥后得到钼酸铜前驱体,记为产物A;
3)将20mg产物A分散于100mL浓度为0.04mol/L的3-(二丁氨基)苯酚水溶液中,得到反应液,室温下搅拌7h,反应完成后经过滤、清洗、干燥后得到产物B;
4)将产物B在氩气气氛下850℃煅烧2h,得到铜碳化钼碳复合材料。
实施例4
1)配制浓度为0.2mol/L的醋酸铜水溶液和0.08mol/L的钼酸铵水溶液;
2)将钼酸铵水溶液按照1:0.5的体积比滴加到60℃的醋酸铜水溶液中,接着50W超声处理10min,清洗干燥后得到产物A;
3)将20mg产物A分散在100mL浓度为0.03mol/L的4-(2-氨基乙基)-1,2-苯二酚水溶液中,得到反应液,室温下搅拌8h,反应完成后经过滤、清洗、干燥后得到产物B;
4)将产物B在氮气气氛下800℃煅烧2h,得到铜碳化钼碳复合材料。
实施例5
1)分别配制浓度为0.4mol/L的硝酸铜水溶液和0.1mol/L的钼酸钠水溶液;
2)将钼酸钠水溶液按照1:0.5的体积比滴加到50℃的硝酸铜水溶液中,接着70W超声处理30min,清洗干燥后得到钼酸铜前驱体,记为产物A;
3)将20mg产物A分散在100mL浓度为0.02mol/L的4-(2-氨基乙基)-1,2-苯二酚水溶液中,得到反应液,室温下搅拌10h,反应完成后经过滤、清洗、干燥后得到产物B;
4)将产物B在氩气气氛下900℃煅烧2h,得到铜碳化钼碳复合材料。
以上内容仅为说明本发明的技术思想,不能以此限定本发明的保护范围,凡是按照本发明提出的技术思想,在技术方案基础上所做的任何改动,均落入本发明权利要求书的保护范围之内。
Claims (4)
1.一种铜原位掺杂的碳化钼碳复合材料的制备方法,其特征在于,包括以下步骤:
1)配制铜盐水溶液和钼酸盐水溶液;其中,所述铜盐水溶液中铜离子的浓度为0.1-0.4mol/L,所述钼酸盐水溶液中钼酸根离子的浓度为0.05-0.1mol/L;
2)将所述钼酸盐水溶液按体积比为1:(0.5-1)滴加到40-60℃的铜盐水溶液中,得到的混合液,将混合液在50-70W功率下超声10-30min进行反应,反应结束后进行过滤、清洗、干燥得到产物A;
3)将产物A分散在氨基苯酚衍生物水溶液中,得到反应液,将反应液在室温下搅拌4-10h进行反应,反应结束后经过滤、清洗、干燥后得到产物B;
其中,氨基苯酚衍生物水溶液的浓度为0.01~0.04mol/L,每100mL氨基苯酚衍生物水溶液中加入20mg产物A;
步骤3)中氨基苯酚衍生物为2-羟基-5-甲基乙酰苯胺、3-(二丁氨基)苯酚或4-(2-氨基乙基)-1,2-苯二酚;
4)将产物B在惰性气体的气氛下、800-900℃煅烧2h,得到铜原位掺杂的碳化钼碳复合材料。
2.根据权利要求1所述的铜原位掺杂的碳化钼碳复合材料的制备方法,其特征在于,步骤1)中铜盐为硝酸铜或醋酸铜。
3.根据权利要求1所述的铜原位掺杂的碳化钼碳复合材料的制备方法,其特征在于,步骤1)中钼酸盐为钼酸钠或钼酸铵。
4.一种根据权利要求1-3任一项所述的制备方法制备得到的铜原位掺杂的碳化钼碳复合材料。
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