CN110983361A - 一种限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极及其制备方法和应用 - Google Patents
一种限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极及其制备方法和应用 Download PDFInfo
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 title claims abstract description 58
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- 239000002120 nanofilm Substances 0.000 title claims abstract description 52
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 50
- 239000010941 cobalt Substances 0.000 title claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
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Abstract
本发明公开了一种限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极及其制备方法和应用。本发明先合成氧化钽纳米薄膜,然后将其作为载体,通过水热法,负载上Co(tzbc)2(H2O)4配合物,通过化学气相沉积(CVD)的方法,对合成的复合材料进行氮化反应,自然冷却到室温即可制备得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。本发明制备工艺简单,通过CVD炉,不需要特殊压强环境即可完成限域生长钴纳米颗粒的的氮化钽碳纳米薄膜一体化电极的制备。制备的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极同时具有电催化析氢和析氧性能。
Description
技术领域
本发明涉及一种限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极及其制备方法和在电化学领域的应用,属于新材料制备和电化学领域。
背景技术
能源是人类生存与发展的基础,直接影响着各个国家的经济命脉以及全人类的发展方向。目前,能源需求增加与化石燃料燃烧引起的环境恶化之间日益加剧的冲突引发了人们对寻求高效、清洁和可再生替代能源的巨大兴趣。
作为一种丰富的无碳燃料,氢气具有超高的热值,零二氧化碳排放,被认为是未来替代碳基燃料的理想选择。氢能作为一种高效的清洁能源,通过电解水提取出来的氢的总能量是化石燃料热量的9000倍,而目前只有20%左右的氢气来自水分解,主要原因是为了有效降低水电解反应活化能垒,提高反应速率,该过程严重依赖贵金属(如铂、铱、钌)催化剂,这些稀有金属储量少,价格昂贵,无法满足生产需要。随着科学技术的飞速发展,能源存储与转换技术的高效化、器件微型化、高集成、智能化、便携化等方面对材料已经提出了新的更高的要求。因此,开发适用于不同能源存储与转换系统的高效廉价电极材料迫在眉睫。
过渡金属氮化物具有3d价电子壳层结构,其独特的结构、优异的电子性能以及富氧化还原反应等特性,使他们作为电化学活性材料从其他材料中脱颖而出。其中钽的氮化物有很多,包括Ta4N、Ta2N、TaN、Ta4N5、Ta3N5,制备出来的氮化钽材料,由于元素N的插入,致使金属晶格扩张,金属表面态密度增加。这种变化使得金属氮化物具有独特的物理及化学性能:高硬度、高熔点、高温稳定性、高热导率、优异的光学、磁学和电学性能。尤其作为电催化剂在电催化产氢产氧方面,大多数过渡金属氮化物对氢和氧有较高的亲和能力。
纵观文献和专利,传统的氮化钽大多是通过化学气相沉积、磁控反应溅射沉积、离子束增强沉积、脉冲激光沉积法制备得到的材料,都主要应用于光催化以及光电催化反应。Ela Nurlaela等人通过化学气相沉积制备了负载CoOX的氮化钽纳米颗粒(Chem. Mater.2015, 27, 5685−5694);Wang等人通过阳极氧化钽化学气相沉积氮化制备了氮化坦纳米薄膜(Chem. Commun., 2017,53, 11763);制备出来的氮化钽均为应用于光催化的光滑的柱状纳米薄膜阵列但并无良好的电催化性能。
发明内容
本发明旨在提供一种限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极及其制备方法和应用。
本发明以金属钽箔作为模板和钽源,在不额外加入钽盐的情况下,首次采用三步法(阳极氧化—水热限域生长—化学气相氮化)直接在钽箔上生长氮化坦,制备了一体化限域生长钴纳米颗粒的氮化钽碳纳米薄膜电极,所得氮化钽薄膜电极可作为析氢催化剂、析氧催化剂电极。阳极氧化的钽箔不仅可以为氮化坦提供钽源,而且可以作为导电基底,稳固材料,从而提高其容量、催化活性和循环稳定性。
本发明提供了一种限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的制备方法,先合成氧化钽纳米薄膜,然后将其作为载体,通过水热法将Co(tzbc)2(H2O)4配合物限域生长在氧化钽纳米孔道内,再通过化学气相沉积法一步合成限域生长钴纳米颗粒的管壁为镂空的氮化钽碳纳米薄膜一体化电极,且具有稳定的结构形貌。
上述的制备方法具体包括以下步骤:
(1)阳极处理:将20-320平方毫米的钽箔分别用丙酮和乙醇超声清洗,除去表面的有机物,氮气吹干;将清洗后的镍箔作为阳极,铂片作为阴极,阴阳极表面积比例控制在1:1~6:1之间,采用10-70 V直流恒压在溶有0.1-0.3 mol/L NH4F和14.0-16.0 mol/L H2SO40.5-0.8mol/L H2O的浓硫酸的电解液中阳极氧化10-100分钟,清洗后用氮气吹干,得到多孔阳极氧化钽;
(2)于氧化钽纳米阵列孔道中限域生长Co(tzbc)2(H2O)4配合物:将4-(1H-1,2,4-三唑-1-基)苯甲酸(tzbc)(0.015- 0.050g)和Co(NO3)2·6H2O (0.050-0.150g)溶于无水乙醇和H2O的混合溶剂里,将磁力搅拌子沉于溶剂底部,将步骤(1)中得到的多孔氧化钽放于立方铜笼中且悬浮于溶剂中上部,在磁力搅拌器上于空气气氛下混合均匀,接着将溶液及多孔氧化钽转移到具有聚四氟乙烯材质衬底的反应釜中封装好,放入130oC的烘箱中加热24-72h,然后取出在空气中缓慢冷却至室温;然后取出多孔氧化钽并用乙醇洗涤,干燥;
(3)CVD氮化反应:将步骤(2)中得到的多孔氧化钽放在CVD管式炉的石英管中央,设置炉温为550-950 oC,氩气气体流量为50-200 sccm,氨气气体流量10-60sccm,总气压为0.25-0.4 Kpa进行氮化反应,反应时间0.5-5 h,然后在保持氩气气氛下,自然冷却到室温,得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
在化学沉积过程中,反应气为氨气,在氩气、氨气存在下匀速升温至550-950 oC后,采用化学沉积的方法。
所述氮化时间为1h~3h。
本发明提供了一种由上述制备方法制得的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
本发明提供了上述限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极在碱性电解水中催化析氢、催化析氧以及酸性电解水中析氢中的应用。
所述的应用,包括以下步骤:使用三电极体系在电化学工作站上进行电化学测量;使用封口膜和导线将一体化电极封装,直接用作工作电极。
本发明的有益效果:
(1)本发明制备的复合电极中,阳极氧化金属钽箔作为导电基底的同时,还提供钽源,成本低,制备工艺简单,氮化钽直接均匀地生长在钽箔上,有效提高了电极结构的机械稳定性;
(2)本发明制备的一体化电极,与传统工艺相比,在制备电极过程中无需加入导电剂、粘结剂等辅助材料。所得电极材料可以直接应用于电解水催化中,作为电解水催化电极时,不需要研磨、制备浆料、干燥等操作过程,无需引入额外的导电基底,且具有高催化性能、长循环寿命、高容量和高循环稳定性的优势;
(3)本工艺制备的限域生长钴纳米颗粒的氮化钽碳纳米薄膜的载体是镂空多孔的氮化钽纳米柱阵列有别于传统的光滑柱阵列,增大了氮化钽的活性比表面积,同时也易于电解液的渗透,有利于电子的传导;
(4)本工艺制备得到的限域生长钴纳米颗粒的氮化钽碳纳米薄膜材料具有电催化析氢和析氧催化性能,即活性高、起始电势低,电流密度大、塔菲尔斜率小、性能稳定等。
附图说明
图1为实施例1所得产物的XRD图;
图2为实施例2所得产物的SEM图;
图3是实施例3所得产物的TEM图;
图4为实施例4所得产物的 XPS图;
图5是实施例5所得产物应用于电化学碱性析氢反应时的a极化曲线图和b塔菲曲线图;
图6是实施例5所得产物应用于电化学酸性析氢反应时的a极化曲线图和b塔菲曲线图;
图7是实施例5所得产物应用于电化学碱性析氧反应时的a极化曲线图和b塔菲曲线图;
图8是实施例5所得产物在氢气饱和下1.0 M KOH 溶液和0.5 M H2SO4溶液中析氢反应的计时电压曲线。
具体实施方式
下面通过实施例来进一步说明本发明,但不局限于以下实施例。
实施例1:
(1)阳极处理:将1平方厘米的钽箔分别用丙酮和乙醇超声清洗,除去表面的有机物,氮气吹干;以暴露面直径为0.5平方厘米,面积为0.19625平方厘米的圆形钽箔作为阳极,0.27mol/L NH4F和15.89 mol/L H2SO4的电解液,铂片作为阴极,在电压为60 V下阳极氧化15分钟。反应结束后,样品用流动蒸馏水冲洗干净,用氮气吹干,得到多孔阳极氧化钽;
(2)于氧化钽纳米阵列孔道中限域生长Co(tzbc)2(H2O)4配合物:将4-(1H-1,2,4-三唑-1-基)苯甲酸(tzbc)(0.038 g,0.2 mmol)和Co(NO3)2·6H2O (0.119g,0.4 mmol)溶于无水乙醇(4 ml)和H2O (2.5 ml)的混合溶剂里,放入磁子沉于溶剂底部,将步骤(1)中得到多孔氧化钽放于立方铜笼中且悬浮于溶剂中上部,在磁力搅拌器上于空气气氛下保持约二十分钟,接着将溶液及多孔氧化钽转移到具有聚四氟乙烯材质衬底的反应釜中封装好,放入130oC的烘箱中加热,然后取出在空气中缓慢冷却至室温;然后取出多孔氧化钽并用乙醇洗涤,干燥。
(3)CVD氮化反应:将步骤(2)中得到多孔氧化钽放在CVD管式炉的石英管中央,设置炉温为800 oC,氩气气体流量为50 sccm,氨气气体流量20sccm,总气压为0.35 Kpa进行氮化反应,反应时间1h,然后在保持氩气气氛下,自然冷却到室温,得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
图1示出了本实施例所得产物的XRD图,为该材料的XRD图谱与标准卡片库中氮化钽(JCPDS No.19-1291)的(002)、(111)、(110)、(025)和(510)晶面,单质Co (JCPDS No.15-0806)的(111)和(220)的晶面和单质钽(JCPDS No.04-0788)相对应,说明制得的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极除了单质钽、氮化钽和钴纳米晶体外,不含其它杂相。
实施例2
(1)阳极处理:将1平方厘米的钽箔分别用丙酮和乙醇超声清洗,除去表面的有机物,氮气吹干;以暴露面直径为0.5平方厘米,面积为0.19625平方厘米的圆形钽箔作为阳极,0.27mol/L NH4F和15.89 mol/L H2SO4的电解液,铂片作为阴极,在电压为60 V下阳极氧化15分钟。反应结束后,样品用流动蒸馏水冲洗干净,用氮气吹干,得到多孔阳极氧化钽;
(2)于氧化钽纳米阵列孔道中限域生长Co(tzbc)2(H2O)4配合物:将4-(1H-1,2,4-三唑-1-基)苯甲酸(tzbc)(0.038 g,0.2 mmol)和Co(NO3)2·6H2O (0.119g,0.4 mmol)溶于无水乙醇(4 ml)和H2O (2.5 ml)的混合溶剂里,放入磁子沉于溶剂底部,将步骤(1)中得到多孔氧化钽放于立方铜笼中且悬浮于溶剂中上部,在磁力搅拌器上于空气气氛下保持约二十分钟,接着将溶液及多孔氧化钽转移到具有聚四氟乙烯材质衬底的反应釜中封装好,放入130℃的烘箱中加热,然后取出在空气中缓慢冷却至室温;然后取出多孔氧化钽并用乙醇洗涤,干燥。
(3)CVD氮化反应:将步骤(2)中得到多孔氧化钽放在CVD管式炉的石英管中央,设置炉温为800 ℃,氩气气体流量为50 sccm,氨气气体流量20sccm,总气压为0.35 Kpa进行氮化反应,反应时间1h,然后在保持氩气气氛下,自然冷却到室温,得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
图2示出了本实施例所得产物的SEM图,可以看出其形貌为Co纳米颗粒限域生长于多孔的氮化钽纳米管道内,且氮化钽纳米管道之间还有钴纳米棒连接。
实施例3
(1)阳极处理:将1平方厘米的钽箔分别用丙酮和乙醇超声清洗,除去表面的有机物,氮气吹干;以暴露面直径为0.5平方厘米,面积为0.19625平方厘米的圆形钽箔作为阳极,0.27mol/L NH4F和15.89 mol/L H2SO4的电解液,铂片作为阴极,,在电压为60 V下阳极氧化15分钟。反应结束后,样品用流动蒸馏水冲洗干净,用氮气吹干,得到多孔阳极氧化钽;
(2)于氧化钽纳米阵列孔道中限域生长Co(tzbc)2(H2O)4配合物:将4-(1H-1,2,4-三唑-1-基)苯甲酸(tzbc)(0.038 g,0.2 mmol)和Co(NO3)2·6H2O (0.119g,0.4 mmol)溶于无水乙醇(4 ml)和H2O (2.5 ml)的混合溶剂里,放入磁子沉于溶剂底部,将步骤(1)中得到多孔氧化钽放于立方铜笼中且悬浮于溶剂中上部,在磁力搅拌器上于空气气氛下保持约二十分钟,接着将溶液及多孔氧化钽转移到具有聚四氟乙烯材质衬底的反应釜中封装好,放入130℃的烘箱中加热,然后取出在空气中缓慢冷却至室温;然后取出多孔氧化钽并用乙醇洗涤,干燥。
(3)CVD氮化反应:将步骤(2)中得到多孔氧化钽放在CVD管式炉的石英管中央,设置炉温为800℃,氩气气体流量为50 sccm,氨气气体流量20sccm,总气压为0.35 Kpa进行氮化反应,反应时间1h,然后在保持氩气气氛下,自然冷却到室温,得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
图3所示,为本实施例制备的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的不同分辨率下的TEM形貌图,可以看出样品中的氮化钽的管壁是多孔镂空结构,其晶格间距是0.53 nm,属于氮化钽的(002)晶面;钴纳米颗粒的晶格间距是0.21 nm,属于立方晶系金属Co的(111)晶面,这与XRD结果一致,说明Co纳米颗粒的结晶度很高;包裹着Co纳米颗粒的碳层之间的间距是0.35 nm,大于石墨烯的层间距(0.34 nm),属于石墨化的碳层结构。
实施例4
(1)阳极处理:将1平方厘米的钽箔分别用丙酮和乙醇超声清洗,除去表面的有机物,氮气吹干;以暴露面直径为0.5平方厘米,面积为0.19625平方厘米的圆形钽箔作为阳极,0.27mol/L NH4F和15.89 mol/L H2SO4的电解液,铂片作为阴极,,在电压为60 V下阳极氧化15分钟。反应结束后,样品用流动蒸馏水冲洗干净,用氮气吹干,得到多孔阳极氧化钽;
(2)于氧化钽纳米阵列孔道中限域生长Co(tzbc)2(H2O)4配合物:将4-(1H-1,2,4-三唑-1-基)苯甲酸(tzbc)(0.038 g,0.2 mmol)和Co(NO3)2·6H2O (0.119g,0.4 mmol)溶于无水乙醇(4 ml)和H2O (2.5 ml)的混合溶剂里,放入磁子沉于溶剂底部,将步骤(1)中得到多孔氧化钽放于立方铜笼中且悬浮于溶剂中上部,在磁力搅拌器上于空气气氛下保持约二十分钟,接着将溶液及多孔氧化钽转移到具有聚四氟乙烯材质衬底的反应釜中封装好,放入130℃的烘箱中加热,然后取出在空气中缓慢冷却至室温;然后取出多孔氧化钽并用乙醇洗涤,干燥。
(3)CVD氮化反应:将步骤(2)中得到多孔氧化钽放在CVD管式炉的石英管中央,设置炉温为800 oC,氩气气体流量为50 sccm,氨气气体流量20sccm,总气压为0.35 Kpa进行氮化反应,反应时间1h,然后在保持氩气气氛下,自然冷却到室温,得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
如图4所示,为本实施例制备的含氮掺杂的钴基碳纳米材料的XPS谱图,图4a为该限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的XPS全谱扫描图,表明该限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极中含有Ta、Co、N、C、O,其中Co、C、O和部分N来自于三唑-钴配合物的分解,Ta和部分N来自于氮化钽;图4b为C元素扫描图,表明材料中含有碳;图4c为Ta元素扫描图,主要来自氮化钽;图4d为N元素扫描图;图4e为Co元素扫描图表明限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极中含有钴纳米颗粒。
实施例5:应用
(1)阳极处理:将1平方厘米的钽箔分别用丙酮和乙醇超声清洗,除去表面的有机物,氮气吹干;以暴露面直径为0.5平方厘米,面积为0.19625平方厘米的圆形钽箔作为阳极,0.27mol/L NH4F和15.89 mol/L H2SO4的电解液,铂片作为阴极,在电压为60 V下阳极氧化15分钟。反应结束后,样品用流动蒸馏水冲洗干净,用氮气吹干,得到多孔阳极氧化钽;
(2)于氧化钽纳米阵列孔道中限域生长Co(tzbc)2(H2O)4配合物:将4-(1H-1,2,4-三唑-1-基)苯甲酸(tzbc)(0.038 g,0.2 mmol)和Co(NO3)2·6H2O (0.119g,0.4 mmol)溶于无水乙醇(4 ml)和H2O (2.5 ml)的混合溶剂里,放入磁子沉于溶剂底部,将步骤(1)中得到多孔氧化钽放于立方铜笼中且悬浮于溶剂中上部,在磁力搅拌器上于空气气氛下保持约二十分钟,接着将溶液及多孔氧化钽转移到具有聚四氟乙烯材质衬底的反应釜中封装好,放入130℃的烘箱中加热,然后取出在空气中缓慢冷却至室温;然后取出多孔氧化钽并用乙醇洗涤,干燥。
(3)CVD氮化反应:将步骤(2)中得到多孔氧化钽放在CVD管式炉的石英管中央,设置炉温为800 ℃,氩气气体流量为50 sccm,氨气气体流量20sccm,总气压为0.35 Kpa进行氮化反应,反应时间1h,然后在保持氩气气氛下,自然冷却到室温,得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
下面通过实验验证实施例5所得材料在电化学领域中的应用:
碱性电催化析氢性能测试:
为了研究材料的析氢催化性能,使用三电极体系在上海辰华CHI-660E型号的电化学工作站上进行测试。以1mol/L KOH水溶液为电解液,高纯铂片作为对电极,饱和KCl溶液的Hg/Hg2Cl2电极作为参比电极,限域生长钴纳米颗粒的氮化钽碳纳米薄膜作为工作电极(暴露有效面积为0.19625平方厘米),以氢气鼓泡30分钟,除去溶解氧,以50 mV/s扫速进行极化曲线测量,所有电势换成标准氢电极(RHE):E(RHE)= E(SCE)+(0.242 + 0.059pH)。如图5a所示为极化曲线,限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的始析氢电位为42mV左右,当电流达到10 mA/cm2时的过电势为91 mV,如图5b所示,为塔菲尔曲线,可以看出,该材料较具有较低的塔菲尔斜率,约为72mV/dec。
酸性电催化析氢性能测试:
为了研究材料的析氢催化性能,使用三电极体系在上海辰华CHI-660E型号的电化学工作站上进行测试。以0.5mol/L H2SO4水溶液为电解液,高纯铂片作为对电极,饱和KCl溶液的Hg/Hg2Cl2电极作为参比电极,限域生长钴纳米颗粒的氮化钽碳纳米薄膜作为工作电极(暴露有效面积为0.19625平方厘米),以氢气鼓泡30分钟,除去溶解氧,以50 mV/s扫速进行极化曲线测量,所有电势换成标准氢电极(RHE):E(RHE)= E(SCE)+(0.242 + 0.059pH)。如图6a所示,限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的起始析氢电位为10 mV左右,当电流达到10 mA/cm2时的过电势为51 mV,如图6b所示,该材料较具有较低的塔菲尔斜率,为55mV/dec。
电催化析氧性能测试:
使用三电极体系在上海辰华CHI-660E型号的电化学工作站上进行材料的析氧催化性能的测试。以1 mol/L KOH水溶液为电解液,高纯铂片作为对电极,饱和KCl溶液的Hg/Hg2Cl2电极作为参比电极,限域生长钴纳米颗粒的氮化钽碳纳米薄膜为工作电极(暴露有效面积为0.19625平方厘米),以纯氧气鼓泡30分钟,除去溶解氧,以5 mV/s扫速进行极化曲线测量,所有电势换成标准氢电极(RHE):E(RHE)= E(SCE)+(0.242 + 0.059pH)。如图7a所示,为事例4的极化曲线,可以看出在电流密度为10 mA cm-2时过电势为350 mV(1.58V相对标准氢电极),如图7b所示,为塔菲尔曲线,可以看出本发明制备的材料具有低的Tafel斜率,约为60.5 mV dec-1。
稳定性测试:如图8所示,是本发明制备的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极在氢气饱和的0.5 M H2SO4溶液和的1 M KOH 溶液中的计时电压曲线。从图8可以看出,本发明制备的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极在恒电位下经过25h的测试,极化电流与初始值相比几乎没有衰减,显示出良好的稳定性。
本工艺制备的限域生长钴纳米颗粒的氮化钽碳纳米薄膜材料的金属Co纳米颗粒镶嵌在石墨化碳层(Co@NC)中,X射线粉末衍射(XRD)、X射线光电子能谱 (XPS) 表明该材料中包含Ta、Co、C、和N元素存在;透射电子显微镜 (TEM) 形貌图表明,氮化钽为镂空多孔的纳米管道,生成的钴纳米晶体结晶程度高,具有蓬松的石墨化层也有利于电子的传导;此外,由于Co纳米颗粒被包裹在碳层里,缓解了其在电解液中的逐渐腐蚀,进而提高了材料在电解液中的稳定性能。
Claims (9)
1.一种限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的制备方法,其特征在于:先合成氧化钽纳米薄膜,然后将其作为载体,通过水热法将Co(tzbc)2(H2O)4配合物限域生长在氧化钽纳米孔道内,再通过化学气相沉积法一步合成限域生长钴纳米颗粒的管壁为镂空的氮化钽碳纳米薄膜一体化电极,且具有稳定的结构形貌。
2.根据权利要求1所述的限域生长钴纳米颗粒的氮化钽碳纳米薄膜催化剂的制备方法,其特征在于:具体包括以下步骤:
(1)阳极处理:将20-320平方毫米的钽箔分别用丙酮和乙醇超声清洗,除去表面的有机物,氮气吹干;将清洗后的镍箔作为阳极,铂片作为阴极,阴阳极表面积比例控制在1:1~6:1之间,采用10-70 V直流恒压在溶有0.1-0.3 mol/L NH4F和14.0-16.0 mol/L H2SO4电解液中阳极氧化10-100分钟,清洗后用氮气吹干,得到多孔阳极氧化钽;
(2)于氧化钽纳米阵列孔道中限域生长Co(tzbc)2(H2O)4配合物:将0.015- 0.050g4-(1H-1,2,4-三唑-1-基)苯甲酸(tzbc)和0.050-0.150gCo(NO3)2·6H2O溶于无水乙醇和H2O的混合溶剂里,将磁力搅拌子沉于溶剂底部,将步骤(1)中得到的多孔阳极氧化钽放于立方铜笼中且悬浮于溶剂中上部,在磁力搅拌器上于空气气氛下混合均匀,接着将溶液及多孔阳极氧化钽转移到反应釜中封装好,放入130oC的烘箱中加热24-72h,然后取出在空气中缓慢冷却至室温;取出多孔阳极氧化钽并用乙醇洗涤,干燥;
(3)CVD氮化反应:将步骤(2)中得到的多孔阳极氧化钽放在CVD管式炉的石英管中央,设置炉温为550-950 oC,通入氩气和氨气,总气压为0.25-0.4 kPa进行氮化反应,反应时间0.5-5 h,然后在保持氩气气氛下,自然冷却到室温,得到限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
3.根据权利要求2所述的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的制备方法,其特征在于:所述反应釜为具有聚四氟乙烯材质衬底的反应釜。
4.根据权利要求2所述的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的制备方法,其特征在于:在化学沉积过程中,反应气为氨气,在氩气、氨气存在下匀速升温至550-950 oC。
5.根据权利要求4所述的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的制备方法,其特征在于:氩气气体流量为50-200 sccm,氨气气体流量10-60sccm。
6.根据权利要求2所述的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极的制备方法,其特征在于:所述氮化时间为1h~3h。
7.一种权利要求1~6任一项所述的制备方法制得的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极。
8.一种权利要求7所述的限域生长钴纳米颗粒的氮化钽碳纳米薄膜一体化电极在碱性电解水中催化析氢、催化析氧以及酸性电解水中析氢中的应用。
9.根据权利要求8所述的应用,其特征在于包括以下步骤:使用三电极体系在电化学工作站上进行电化学测量;使用封口膜和导线将一体化电极封装,直接用作工作电极。
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