CN105140535B - 硫化钴/氮硫共掺杂碳空心球复合材料及其制备方法 - Google Patents
硫化钴/氮硫共掺杂碳空心球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 82
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 6
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- 230000005540 biological transmission Effects 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
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- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 3
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- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
一种硫化钴/氮硫共掺杂碳空心球复合材料及其制备方法,属于燃料电池电催化剂及其制备技术领域。该复合材料由直径1‑2微米的氮硫共掺杂碳空心球和直径3‑20纳米的硫化钴Co9S8颗粒组成;其中,氮硫共掺杂碳空心球由相互连接且厚度为10‑20纳米、径向尺寸为200‑500纳米的碳纳米片组成,Co9S8颗粒均匀地负载在碳纳米片上。该复合材料制备方法:在水热条件下将含氮硫的有机小分子阴离子插入层状双羟基复合金属氧化物层间以获得插层结构前驱体,再经高温煅烧及酸化反应获得Co9S8/氮硫共掺杂碳空心球。优点在于,该复合材料表现出优异的电催化氧还原活性;并制备方法环保无毒、工艺简单。
Description
技术领域
本发明属于燃料电池电催化剂及其制备技术领域,特别是涉及一种硫化钴/氮硫共掺杂碳空心球复合材料及其制备方法,即硫化钴Co9S8和氮硫共掺杂碳空心球的复合材料及其制备方法。
背景技术
燃料电池由于其高能量转换效率和环境友好等优点引起了研究者的关注,有望广泛应用于电动车和便携电子设备。阴极氧还原催化剂是影响燃料电池性能及成本的重要组成部分。虽然Pt基催化剂表现出优异的氧还原催化活性,但是由于Pt金属价格昂贵、储量少及稳定性差等原因阻碍了燃料电池的商业化。因此,开发基于非贵金属的高效氧还原电催化剂日益迫切。
对碳材料进行杂原子掺杂可以改变碳材料的电子结构和化学性质,使其表现出良好的电催化氧还原活性;具有多级结构的多孔碳材料可以提高碳材料的有效比表面积,增加反应物的传递速率,从而可以进一步提高杂原子掺杂碳材料的电催化氧还原活性。在文献(1)Angew Chem Int Ed,2014,53,1570-1574中,Wei Wei等人制备了具有特定介孔尺寸的氮掺杂碳纳米片,表现出良好的电催化氧还原活性。
金属硫化物作为氧还原电催化剂也具有非常广阔的应用前景,但是由于其较大的颗粒尺寸和差的导电性限制了其电催化性能的发挥。因此,将金属硫化物和碳材料复合可以有效地提高其电催化性能。在文献(2)Angew Chem Int Ed,2011,50,10969-10972中,Hailiang Wang等人将硫化钴Co1-xS与石墨烯复合,表现出良好的电催化氧还原活性。由于金属硫化物及碳材料种类繁多,二者复合的形式及微观结构也多种多样,因此设计合理的金属硫化物与碳复合材料的组成与微观结构以提升其电催化性能具有重要应用价值。
另外,从制备方法看,已报道文献在制备金属硫化物时通常会涉及硫化氢、二氧化硫、噻吩等有毒且危险的硫源,在制备掺杂碳材料时通常也会涉及氨气、吡啶、乙腈等毒性原料。因此研究开发工艺简单、绿色环保的金属硫化物与掺杂碳复合材料的制备方法具有实际应用价值。
发明内容
本发明的目在于提供一种硫化钴/氮硫共掺杂碳空心球复合材料及其制备方法,设计合理的金属硫化物与碳复合材料的组成与微观结构以提升其电催化性能具有重要应用价值,而研究开发工艺简单、绿色环保的制备方法具有实际应用价值。
硫化钴/氮硫共掺杂碳空心球复合材料的结构示意图如图1所示,该复合材料由直径1-2μm的氮硫共掺杂碳空心球和直径3-20nm的硫化钴Co9S8颗粒组成;其中,氮硫共掺杂碳空心球由相互连接且厚度为10-20nm、径向尺寸为200-500nm的碳纳米片组成,碳纳米片上具有小于2nm的微孔和2-50nm介孔,Co9S8颗粒均匀地负载在碳纳米片上;氮硫共掺杂碳中C/N原子比为10-50,C/S原子比为20-70,Co9S8在复合材料中所占质量百分数为5-20%。
本发明硫化钴/氮硫共掺杂碳空心球复合材料的制备方法是在水热条件下将含氮硫的有机小分子阴离子插入层状双羟基复合金属氧化物层间以获得插层结构前驱体,再经高温煅烧及酸化反应获得Co9S8/氮硫共掺杂碳空心球,具体工艺步骤为:
(1)将二价金属离子M2+的可溶性盐、三价金属离子M'3+的可溶性盐、六次甲基四胺及氟化铵混合,溶于脱二氧化碳的去离子水中配制得到混合溶液;在氮气保护下将上述混合溶液与含氮硫的有机小分子阴离子A-的可溶性盐混合,转入水热反应釜中在80-120℃温度下反应8-24h;将反应后得到的悬浊液过滤,用去离子水和乙醇洗涤滤饼至滤液pH值为7-7.5,然后将滤饼在60-80℃干燥6-12h,得到具有插层结构的层状双羟基复合金属氧化物;其中,所述二价金属离子M2+的可溶性盐为Co的硝酸盐、硫酸盐、草酸盐或氯化物中的一种或多种,所述三价金属离子M'3+的可溶性盐为Al的硝酸盐、硫酸盐、草酸盐或氯化物中的一种或多种;所述混合溶液中二价金属离子M2+与三价金属离子M'3+的物质的量的比为2-4:1,且二价金属离子M2+和三价金属离子M'3+的总浓度为0.1-0.4mol/L;所述六次甲基四胺的物质的量为所述二价金属离子M2+和三价金属离子M'3+总物质的量的1.25倍;所述氟化铵的物质的量与所述二价金属离子M2+和三价金属离子M'3+总物质的量相等;所述含氮硫的有机小分子阴离子A-的可溶性盐为间氨基苯磺酸钠、对氨基苯磺酸钠、邻氨基苯磺酸钠中的一种,且含氮硫的有机小分子阴离子A-与二价金属离子M2+的物质的量之比为3-4:1。
(2)在氮气或氩气气氛下,将(1)中插层结构层状双羟基复合金属氧化物以2-10℃/min速率升温至700-1000℃煅烧1-10h,自然冷却至室温,得到煅烧产物。
(3)按照2-5g/L的固液比将(2)中煅烧产物置于稀酸溶液中酸化处理12-48h,将反应后得到的悬浊液过滤,用去离子水洗涤滤饼至滤液pH值为6.8-7,然后将所得黑色沉淀在60-80℃干燥6-12h,即得到Co9S8/氮硫共掺杂碳空心球;其中,所述稀酸溶液为盐酸、硫酸中的一种且稀酸溶液的质量百分比浓度为5-20%。
图2的X射线衍射(XRD)图表明本发明产品为Co9S8和碳材料的复合物,没有出现其他杂质相,且晶型良好。图3的透射电镜(TEM)照片表明本发明产品是直径为1-2μm的空心球,该空心球由相互连接且厚度为10-20nm、径向尺寸为200-500nm的碳纳米片和均匀负载在碳纳米片上的Co9S8颗粒构成。图4的高分辨透射电镜(HRTEM)照片可以看到构成空心碳纳米球的片层上具有丰富的5-30nm的介孔,3-20nm的Co9S8颗粒均匀地负载在碳纳米片层上。图5是本发明产品的孔径分布测试结果,表明存在小于2nm的微孔、2-50nm介孔及50nm以上大孔。图6的X-射线光电子能谱(XPS)测试结果表明本发明产品含有C,N,S,Co,O等元素。图7和图8的电化学测试结果表明本发明提供的硫化钴Co9S8/氮硫共掺杂碳空心球复合材料具有优异的电催化氧还原活性。
本发明的显著特点及优势在于:本发明提供了一种硫化钴Co9S8/氮硫共掺杂碳空心球复合材料,该复合材料由多孔氮硫共掺杂碳纳米片和均匀分布在碳纳米片上的Co9S8纳米颗粒构成,基于其独特微观结构及组成,该复合材料表现出优异的电催化氧还原活性。另外,本发明制备方法也具有工艺简单,生产成本低,安全无环境污染等优点。
附图说明
图1为本发明提供的硫化钴Co9S8/氮硫共掺杂碳空心球复合材料的结构示意图。
图2为本发明实施例1提供的Co9S8/氮硫共掺杂碳空心球复合材料的XRD谱图;其中,横坐标为角度2θ,单位为:度(°);纵坐标为衍射强度,单位为:绝对单位(a.u.)。
图3为本发明实施例1提供的Co9S8/氮硫共掺杂碳空心球复合材料的透射电镜
照片。
图4为本发明实施例1提供的Co9S8/氮硫共掺杂碳空心球复合材料的高分辨透射电镜照片。
图5为本发明实施例1提供的Co9S8/氮硫共掺杂碳空心球复合材料的孔径分布图;其中,横坐标为孔尺寸,单位为:纳米(nm);纵坐标为孔体积,单位为:厘米3/(克·纳米)(cm3/(g·nm))。
图6为本发明实施例1提供的Co9S8/氮硫共掺杂碳空心球复合材料的X-射线光电子能谱图;其中,横坐标为结合能,单位为:电子伏特(eV);纵坐标为强度,单位为:绝对单位(a.u.)。
图7为本发明实施例1提供的Co9S8/氮硫共掺杂碳空心球复合材料分别在氮气和氧气气氛下电极表面发生氧还原反应的循环伏安曲线;其中,横坐标为相对于可逆氢电极的电位,单位为:伏特(V);纵坐标为电流密度,单位为:毫安每平方厘米(mA/cm2)。
图8为本发明实施例1提供的Co9S8/氮硫共掺杂碳空心球复合材料在不同旋转圆盘电极转速下电极表面发生氧还原反应的线性扫描伏安曲线;其中,横坐标为相对于可逆氢电极的电位,单位为:伏特(V);纵坐标为电流密度,单位为:毫安每平方厘米(mA/cm2)。
具体实施方式:
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及具体实施例,对本发明进行进一步详细说明,但是本发明不仅限于此。
实施例1
(1)首先将6mmol Co(NO3)2·6H2O,2mmol Al(NO3)3·9H2O,10mmol六次甲基四胺混合和8mmol NH4F混合,溶于20mL脱二氧化碳的去离子水中配制得到混合溶液;然后将20mmol间氨基苯磺酸和20mmolNaOH溶于20mL脱二氧化碳的去离子水中进行中和反应,得到间氨基苯磺酸钠溶液。在氮气保护下将上述混合溶液和间氨基苯磺酸钠溶液进行混合,搅拌均匀后转移至50mL的聚四氟乙烯衬底的高压反应釜中,放入烘箱中在100℃恒温反应12h,取出高压反应釜自然冷却至室温,用800mL去离子水和200mL乙醇抽滤洗涤至滤液pH值为7,然后将滤饼在80℃鼓风干燥8小时,得到间氨基苯磺酸根插层的钴铝双羟基复合金属氧化物。
(2)将上述制备的间氨基苯磺酸根插层的钴铝双羟基复合金属氧化物放入瓷舟后置于石英管式炉中间加热区域,通入纯度≥99%的氮气除氧,30min后,以3℃/min升温速率加热至900℃并保温2h;然后缓慢降至室温,在瓷舟底部生成黑色煅烧产物。
(3)将50mL 10wt%的盐酸溶液加入到上述0.1g的黑色煅烧产物中,超声2h后并静置24h,将反应后得到的悬浊液过滤,用去离子水洗涤滤饼至滤液pH值为6.8,然后将所得黑色沉淀在70℃鼓风干燥10h,即得到硫化钴Co9S8/氮硫共掺杂碳空心球复合材料。
Co9S8/氮硫共掺杂碳空心球复合材料的X-射线衍射图如图2所示,表明本发明产品为Co9S8和碳材料的复合物,没有出现其他杂质相,且晶型良好。图3是上述Co9S8/氮硫共掺杂碳空心球复合材料的透射电镜照片,从图中可以看出该空心球由相互连接且厚度为10-20nm、径向尺寸为200-500nm的碳纳米片和均匀负载在碳纳米片上的Co9S8颗粒构成。图4的高分辨透射电镜照片可以看到构成碳空心球的片层上具有丰富的5-30nm的介孔以及均匀负载在碳纳米片上3-20nm的Co9S8颗粒;图5是上述Co9S8/氮硫共掺杂碳空心球复合材料的孔径分布测试结果,表明存在小于2nm的微孔、2-50nm介孔以及50nm以上大孔。图6是上述Co9S8/氮硫共掺杂碳空心球复合材料的X-射线光电子能谱图,表明本发明产品含有C,N,S,Co,O等元素,且氮硫共掺杂碳中C/N原子比为30,C/S原子比为26,Co9S8在复合材料中所占质量百分数为16.8%。
实施例2
(1)首先将6mmol CoSO4·7H2O,3mmol Al(NO3)3·9H2O,11.25mmol六次甲基四胺混合和9mmol NH4F混合,溶于30mL脱二氧化碳的去离子水中配制得到混合溶液;然后将24mmol对氨基苯磺酸和24mmolNaOH溶于10mL脱二氧化碳的去离子水中进行中和反应,得到对氨基苯磺酸钠溶液。在氮气保护下将上述混合溶液和对氨基苯磺酸钠溶液进行混合,搅拌均匀后转移至50mL的聚四氟乙烯衬底的高压反应釜中,放入烘箱中在120℃恒温反应8h,取出高压反应釜自然冷却至室温,用去离子水和乙醇抽滤洗涤至滤液pH值为7,然后将滤饼在60℃鼓风干燥12h,得到对氨基苯磺酸根插层的钴铝双羟基复合金属氧化物。
(2)将上述制备的间氨基苯磺酸根插层的钴铝双羟基复合金属氧化物放入瓷舟后置于石英管式炉中间加热区域,通入纯度≥99%的氮气除氧,30min后,以10℃/min升温速率加热至800℃并保温10h;然后缓慢降至室温,在瓷舟底部生成黑色煅烧产物。
(3)将50mL 5wt.%的硫酸溶液加入到上述0.25g的黑色煅烧产物中,超声2h后并静置48h,将反应后得到的悬浊液过滤,用去离子水洗涤滤饼至滤液pH值为7,然后将所得黑色沉淀在80℃鼓风干燥6h,即得到硫化钴Co9S8/氮硫共掺杂碳空心球复合材料。
实施例3
(1)首先将8mmol CoCl2·6H2O,2mmol AlCl3·6H2O,12.5mmol六次甲基四胺混合和10mmol NH4F混合,溶于10mL脱二氧化碳的去离子水中配制得到混合溶液;然后将24mmol邻氨基苯磺酸和24mmolNaOH溶于30mL脱二氧化碳的去离子水中进行中和反应,得到邻氨基苯磺酸钠溶液。在氮气保护下将上述混合溶液和邻氨基苯磺酸钠溶液进行混合,搅拌均匀后转移至50mL的聚四氟乙烯衬底的高压反应釜中,放入烘箱中在80℃恒温反应24h,取出高压反应釜自然冷却至室温,用去离子水和乙醇抽滤洗涤至滤液pH值为7.5,然后将滤饼在70℃鼓风干燥6h,得到邻氨基苯磺酸根插层的钴铝双羟基复合金属氧化物。
(2)将上述制备的邻氨基苯磺酸根插层的钴铝双羟基复合金属氧化物放入瓷舟后置于石英管式炉中间加热区域,通入纯度≥99%的氩气除氧,30min后,以2℃/min升温速率加热至1000℃并保温1h;然后缓慢降至室温,在瓷舟底部生成黑色煅烧产物。
(3)将50mL 10wt.%的盐酸溶液加入到上述0.2g的黑色煅烧产物中,超声2h后并静置36h,将反应后得到的悬浊液过滤,用去离子水洗涤滤饼至滤液pH值为7,然后将所得黑色沉淀在60℃鼓风干燥8h,即得到硫化钴Co9S8/氮硫共掺杂碳空心球复合材料。
为了进一步验证本发明上述实施例提供的Co9S8/氮硫共掺杂碳空心球复合材料的电化学性能,以下选取上述实施例1所得Co9S8/氮硫共掺杂碳空心球复合材料粉体负载在电极表面,并测试其电化学氧还原反应活性。其步骤依次为:
制备工作电极:首先将2.95mg Co9S8/氮硫共掺杂碳空心球复合材料粉体分散在0.3mL去离子水、0.6mL异丙醇和0.1mL 5wt.%Nafion的混合溶液中;将上述混合溶液超声30min得到黑色溶液;取3.75μL的Co9S8/氮硫共掺杂碳空心球复合材料分散液滴在用Al2O3抛光过的3mm玻碳电极上,自然干燥。
实验条件设置:在电化学工作站上,使用三电极体系。采用饱和甘汞电极和铂线作为参比电极和对电极,为了方便,电位均换算成相对于可逆氢电极。在0.1mol/L的KOH电解质溶液中进行循环伏安测试和旋转圆盘电极测试。测试前,电解质溶液通氮气或氧气至少30min。循环伏安测试在1.05V到0.15V(相对于可逆氢电极)电位范围以50mV/s的扫速进行。旋转圆盘电极的线性扫描伏安曲线的测试在1.05V到0.15V(相对于可逆氢电极),400~2500rpm转速下以5mV/s的扫速进行。
图7为氮气饱和与氧气饱和的0.1mol/L KOH溶液中的循环伏安曲线,从图中可以看出,当溶液中充满氮气时,循环伏安曲线没有特征峰出现。当溶液充满氧气时,循环伏安曲线在0.84V(相对于可逆氢电极)出可以看到一个很明显的阴极峰,这个峰是氧气还原的峰,表明Co9S8/氮硫共掺杂碳空心球复合材料对氧气具有催化活性。图8是在不同转速下,Co9S8/氮硫共掺杂碳空心球复合材料的线性扫描伏安曲线。线性扫描伏安曲线显示电流密度随着转速的增加而增长,这是由于在高转速下扩散距离缩短,此外,Co9S8/氮硫共掺杂碳空心球复合材料具有高的半波电位和极限扩散电流密度,表明其具有优异的氧还原电催化性能。
通过对本发明上述实施例提供的Co9S8/氮硫共掺杂碳空心球复合材料电化学性能测试发现,该Co9S8/氮硫共掺杂碳空心球复合材料具有优异的氧还原催化活性,并且表现出优异的抗甲醇毒化和稳定性,有望用于燃料电池。
上述实例只是本发明的举例,尽管为说明目的公开了本发明的最佳实施例和附图,然而并非用于限制本发明,任何熟悉本领域的技术人员,在不脱离本发明及所附的权利要求的精神和范围内,各种替换、变化和修改都是可能的。因此,本发明不应局限于最佳实施例和附图所公开的内容。
Claims (6)
1.一种硫化钴/氮硫共掺杂碳空心球复合材料,其特征在于,该复合材料由直径1-2微米的氮硫共掺杂碳空心球和直径3-20纳米的硫化钴Co9S8颗粒组成;其中,氮硫共掺杂碳空心球由相互连接且厚度为10-20纳米、径向尺寸为200-500纳米的碳纳米片组成,碳纳米片上具有小于2纳米的微孔和2-50纳米介孔,Co9S8颗粒均匀地负载在碳纳米片上;氮硫共掺杂碳中C/N原子比为10-50,C/S原子比为20-70,Co9S8在复合材料中所占质量百分数为5-20%。
2.一种权利要求1所述的硫化钴/氮硫共掺杂碳空心球复合材料的制备方法,其特征在于,包括如下步骤:
(1)将二价金属离子M2+的可溶性盐、三价金属离子M'3+的可溶性盐、六次甲基四胺及氟化铵混合,溶于脱二氧化碳的去离子水中配制得到混合溶液;在氮气保护下将上述混合溶液与含氮硫的有机小分子阴离子A-的可溶性盐混合,转入水热反应釜中在80-120℃温度下反应8-24小时;将反应后得到的悬浊液过滤,用去离子水和乙醇洗涤滤饼至滤液pH值为7-7.5,然后将滤饼在60-80℃干燥6-12小时,得到具有插层结构的层状双羟基复合金属氧化物;
所述二价金属离子M2+的可溶性盐为Co的硝酸盐、硫酸盐、草酸盐或氯化物中的一种或多种,所述三价金属离子M'3+的可溶性盐为Al的硝酸盐、硫酸盐、草酸盐或氯化物中的一种或多种;
(2)在氮气或氩气气氛下,将(1)中插层结构层状双羟基复合金属氧化物以2-10℃/分钟速率升温至700-1000℃煅烧1-10小时,自然冷却至室温,得到煅烧产物;
(3)按照2-5克/升的固液比将(2)中煅烧产物置于稀酸溶液中酸化处理12-48小时,将反应后得到的悬浊液过滤,用去离子水洗涤滤饼至滤液pH值为6.8-7,然后将所得黑色沉淀在60-80℃干燥6-12小时,即得到Co9S8/氮硫共掺杂碳空心球。
3.根据权利要求2所述的制备方法,其特征在于,在步骤(1)中,所述混合溶液中二价金属离子M2+与三价金属离子M'3+的物质的量的比为2-4:1,且二价金属离子M2+和三价金属离子M'3+的总浓度为0.1-0.4摩尔/升。
4.根据权利要求2所述的制备方法,其特征在于,在步骤(1)中,所述六次甲基四胺的物质的量为所述二价金属离子M2+和三价金属离子M'3+总物质的量的1.25倍;所述氟化铵的物质的量与所述二价金属离子M2+和三价金属离子M'3+总物质的量相等。
5.根据权利要求2所述的制备方法,其特征在于,在步骤(1)中,所述含氮硫的有机小分子阴离子A-的可溶性盐为间氨基苯磺酸钠、对氨基苯磺酸钠、邻氨基苯磺酸钠中的一种,且含氮硫的有机小分子阴离子A-与二价金属离子M2+的物质的量之比为3-4:1。
6.根据权利要求2所述的制备方法,其特征在于,在步骤(3)中,所述稀酸溶液为盐酸、硫酸中的一种且稀酸溶液的质量百分比浓度为5-20%。
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