CN110368961B - 一种片层自组装海星状富镍碲化镍催化剂的制备方法 - Google Patents
一种片层自组装海星状富镍碲化镍催化剂的制备方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- NZIHMSYSZRFUQJ-UHFFFAOYSA-N 6-chloro-1h-benzimidazole-2-carboxylic acid Chemical compound C1=C(Cl)C=C2NC(C(=O)O)=NC2=C1 NZIHMSYSZRFUQJ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000001338 self-assembly Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000006260 foam Substances 0.000 claims abstract description 22
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 21
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 22
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- 230000000052 comparative effect Effects 0.000 description 14
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910005913 NiTe Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
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- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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Abstract
本发明涉及电解制氢技术领域,具体公开了一种片层自组装海星状富镍碲化镍催化剂的制备方法,包括以下步骤,步骤1:将氢氧化钾、碲源和还原剂溶解在溶剂中,后加入泡沫镍基底;步骤2:将步骤1密封加热反应,使泡沫镍基底上生成碲化镍,加热的温度不超过200℃;步骤3:将生成有碲化镍的泡沫基底放入惰性气氛中进行退火处理,退火温度不低于250℃,得片层自组装海星状富镍碲化镍催化剂。采用本发明技术方案制得的催化剂呈现海星状富镍结构,有助于提高电解水析氢性能。
Description
技术领域
本发明涉及电解制氢技术领域,特别涉及一种片层自组装海星状富镍碲化镍催化剂的制备方法。
背景技术
电解水制氢,利用不可存储的可再生资源(太阳能、风能、潮汐能等)发电催化水解离析出氢气,不仅获得的产品清洁、纯度高,还可以将电能间接储存为化学能待利用,实现了资源可持续利用,对解决能源和环境问题具有重要意义。因此构筑合适的催化剂是降低电解水制氢能耗、提高电解效率的技术核心。催化剂的作用是加速电极-电解质两相界面上的电荷转移过程。
过渡金属泡沫镍(NF)是常见的电极基底,但基底材料的析氢催化活性较差,通常需要担载具有高催化活性的催化剂。由于析氢反应过程中不断有气泡析出,若催化剂与基底的结合力不牢,催化层容易被析出气体冲刷而脱落,最终导致活性下降甚至失活。因此,对于电极表面的催化剂,首先,需要优化设计催化剂的电子结构,使其有助于氢的吸脱附反应,从而达到高效产氢;其次,催化剂应具备有序化的开放结构,以便提供更多的活性位参与反应,同时为氢的逸出提供通道;最后,催化剂与基底之间的结合力较强,从而增强电子从基底传输到催化剂表面,也避免催化层被产生的气体冲刷而脱落,保证催化电极的稳定性。
发明内容
本发明提供了一种片层自组装海星状富镍碲化镍催化剂的制备方法,其目的在于增加碲化镍催化剂的析氢活性位,提高析氢性能。
为了达到上述目的,本发明的技术方案为:
一种片层自组装海星状富镍碲化镍催化剂的制备方法,包括以下步骤:
步骤1:将氢氧化钾、碲源和还原剂溶解在溶剂中,后加入泡沫镍基底;
步骤2:将步骤1密封加热反应,使泡沫镍基底上生成碲化镍,加热的温度不超过200℃;
步骤3:将生成有碲化镍的泡沫基底放入惰性气氛中进行退火处理,退火温度不低于250℃,得片层自组装海星状富镍碲化镍催化剂。
本技术方案的技术原理和效果在于:
1、本方案中的氢氧化钾作为强碱具有腐蚀性,在密封环境中加热可以加速对泡沫镍基底的腐蚀能力,提高了泡沫镍基底表面的粗糙度,有利于增加泡沫镍基底的活性比表面积和活性位,同时,泡沫镍基底被氢氧化钾腐蚀溶解而自发提供镍离子,无须额外加入镍源,在还原剂水合肼的还原作用下,直接与碲源提供的碲反应生成碲化镍。
2、本方案中由于步骤2中碲化镍在密封状态下加热反应而成,而在步骤3中的退火温度是在惰性气氛中进行的,因此在高温退火时,碲化镍中的镍不会被空气中的氧气氧化而形成氧化镍,镍与碲发生了互相扩散,其中由于镍更容易沿表面和晶界扩散,从而有助于生成表面富含镍的碲化镍,晶体结构由NiTe转变成Ni2.86Te2.0,形成非化学计量配比,而非化学计量配比的产生将有助于形成较多缺陷,改变活性氢物种的吸附脱附性质,增加析氢本征活性。
3、本发明方法制备的片层自组装海星状富镍碲化镍催化剂在未使用粘合剂的情况下,碲化镍与泡沫镍基底之间的结合力强,同时碲化镍催化剂呈现海星状开放结构,电解液和析出气泡易扩散,简单易行,操作安全,适用于氯碱电解、电解水制氢领域,易于实现工业化。
进一步,所述步骤1中的溶剂为乙醇和水的混合液,乙醇与水的体积比为1:2。
有益效果:发明人通过实验证明,采用乙醇与水以1:2的体积比混合的混合液作为溶剂,更利于碲源与泡沫镍基底反应生成碲化镍。
进一步,所述步骤1中氢氧化钾的摩尔浓度为0.1~10mol/L。
有益效果:由于氢氧化钾是用于腐蚀泡沫镍基底的表面,使泡沫基底的表面粗糙度增大,而由于生成的碲化镍为微米级,因此粗糙度又不能太大,所以氢氧化钾在此摩尔浓度下即能保证泡沫镍基底的有一定粗糙度,又能够保证不会过于粗糙。
进一步,所述步骤1中碲源的摩尔浓度为0.001~0.1mol/L。
有益效果:由于碲化镍是在泡沫镍基底的表面生长的,且生成的碲化镍均为微米级,由于碲化镍一旦形成,就相当于在泡沫镍基底的表面形成一层保护层,阻断了泡沫镍基底继续与碲源的接触,因此采用该浓度的碲源不仅能够保证在泡沫镍基底表面形成完整的碲化镍层,同时还避免加入过多碲,以造成不必要的浪费。
进一步,所述步骤1中水合肼与溶剂的体积比为1/30~1/3。
有益效果:采用该体积比的水合肼能够充分利用水合肼的还原作用,使碲源与泡沫镍基底产生充分的反应,形成碲化镍。
进一步,所述步骤1中的碲源为单质碲、氧化碲或亚碲酸钠中的一种。
有益效果:采用这三种碲源均可制得富镍的碲化镍催化剂。
进一步,所述步骤2中加热温度为80~200℃,反应时间为1~36h。
有益效果:在该反应温度和时间下,更有利于形成片层海星状结构的碲化镍。
进一步,所述步骤3中退火温度为250~500℃,退火时间为0.5~10h。
有益效果:生成有碲化镍的泡沫镍基底在该退火温度和退火时间下,镍和碲能够更好的互相扩散,有助于形成表面富镍的碲化镍。
附图说明
图1为实施例1中片层自组装海星状富镍碲化镍催化剂的扫描电子显微镜图;
图2为实施例1中步骤3生成有碲化镍的泡沫镍基底在退火前后的XRD图;
图3为实施例1和对比例1~2的析氢线性扫描伏安曲线图。
具体实施方式
下面通过具体实施方式进一步详细说明:
实施例1-5的参数如下表1所示:
表1为实施例1~5片层自组装海星状富镍碲化镍催化剂制备方法的参数
下面以实施例1为例详细说明一种片层自组装海星状富镍碲化镍催化剂的制备方法,包括以下步骤:
步骤1:以10mL乙醇和20mL水的混合液为溶剂,配制1.0mol/L的氢氧化钾和0.01mol/L的单质碲,加入4mL的水合肼,后向溶液中加入清洗干净的泡沫镍基底。
步骤2:将步骤1密封加热反应,加热的温度为180℃,反应的时间为10h,使泡沫镍基底上生成一层碲化镍,生成有碲化镍的泡沫镍基底的化学表达式记为NiTe/NF。
步骤3:从步骤2溶液中取出的生成有碲化镍的泡沫基底进行洗涤干燥,后放入氩气惰性气氛中进行高温退火处理,退火温度为300℃,退火时间为0.5h,得到片层自组装海星状富镍碲化镍催化剂,化学表达式记为Ni2.86Te2.0/NF。
另列举两组对比例与实施例1~5得到的片层自组装海星状富镍碲化镍催化剂进行对比试验:
对比例1为未生成有碲化镍的泡沫镍(NF)基底。
对比例2采用负载量为20wt%Pt,型号为Johnson Matthey的商业Pt/C催化剂。
现对实施例1~5和对比例1~2进行试验检测:
1、SEM检测:
采用扫描电镜对实施例1~5制得的片层自组装海星状富镍碲化镍催化剂进行检测,以实施例1为例,检测结果如图1所示。
从图1可以观察到,泡沫镍基底的表面形成了均匀的片层自组装海星状结构的碲化镍,而这样的结构有助于增加催化剂的比表面积,提高活性位数目,同时开放的垂直片层结构还能够促进电解液的传输和析氢反应过程中生成气体产物的及时扩散,使得催化剂具备更好的析氢性能。
2、XRD检测
采用X射线衍射仪对实施例1~5中步骤3高温退火前后的生成有碲化镍的泡沫镍基底进行检测,以实施例1和对比例1为例,如图2所示,详细分析如下。
图2中曲线(1)为对比例1(NF)的衍射图,曲线(2)为步骤3退火后形成的Ni2.86Te2.0/NF的衍射图,曲线(3)为步骤3退火前形成的NiTe/NF的衍射图,从图2的曲线(3)可以观察到,在泡沫镍(NF)表面生成了一层片层海星状富镍碲化镍催化剂后,依然保持了NF金属的特性。
同时观察图2中曲线(2)和曲线(3)可知,生成有碲化镍的泡沫镍基底在退火后,NiTe转变成Ni2.86Te2.0,表面镍含量增加,形成非化学计量配比,这将有助于形成较多缺陷,改变活性氢物种的吸附脱附性质,增加析氢本征活性。
3、线性扫描伏安法
采用三电极体系,以1mol/L的KOH水溶液作为电解质溶液,将实施例1~5制备的片层自组装海星状富镍碲化镍催化剂、对比例1的泡沫镍和对比例2的商业Pt/C催化剂作为工作电极,汞/氧化汞电极为参比电极,碳棒为辅助电极,在电化学工作站上测试析氢线性扫描伏安曲线。
图3中曲线a是对比例1的线性扫描伏安曲线,曲线b是实施例1的线性扫描伏安曲线,曲线c是对比例2的线性扫描伏安曲线;通过对图3的观察可知,在电流密度为10mA/cm2时,对比例1(NF)的过电位为161mV,实施例1(片层自组装海星状富镍碲化镍催化剂)的过电位为121mV,对比例2(商业Pt/C催化剂)的过电位为48mV,通过以上数据可以发现将泡沫镍基底表面进行片层自组装形成海星状富镍碲化镍催化剂的析氢活性相较于对比例1显著提高,尽管在电流密度为10mA/cm2时与商业Pt/C催化剂电极的电位差距较大,但是从图中可以明显观察到,富镍碲化镍催化剂的曲线在大电流密度下具有更小的过电位,在接近50mA/cm2时几乎可与商业Pt/C催化剂相媲美。
以上所述的仅是本发明的实施例,方案中公知的具体结构及特性等常识在此未作过多描述。应当指出,对于本领域的技术人员来说,在不脱离本发明结构的前提下,还可以作出若干变形和改进,这些也应该视为本发明的保护范围,这些都不会影响本发明实施的效果和专利的实用性。本申请要求的保护范围应当以其权利要求的内容为准,说明书中的具体实施方式等记载可以用于解释权利要求的内容。
Claims (7)
1.一种片层自组装海星状富镍碲化镍催化剂的制备方法,其特征在于:包括以下步骤:
步骤1:将氢氧化钾、碲源和水合肼溶解在溶剂中,后加入泡沫镍基底;
步骤2:将步骤1密封加热反应,使泡沫镍基底上生成碲化镍,加热的温度不超过200℃;
步骤3:将步骤2生成有碲化镍的泡沫基底放入惰性气氛中进行退火处理,退火温度为250~500℃,退火时间为0.5~10h,得片层自组装海星状富镍碲化镍催化剂。
2.根据权利要求1所述的一种片层自组装海星状富镍碲化镍催化剂的制备方法,其特征在于:所述步骤1中的溶剂为乙醇和水的混合液,乙醇与水的体积比为1:2。
3.根据权利要求1所述的一种片层自组装海星状富镍碲化镍催化剂的制备方法,其特征在于:所述步骤1中氢氧化钾的摩尔浓度为0.1~10mol/L。
4.根据权利要求1所述的一种片层自组装海星状富镍碲化镍催化剂的制备方法,其特征在于:所述步骤1中碲源的摩尔浓度为0.001~0.1mol/L。
5.根据权利要求1所述的一种片层自组装海星状富镍碲化镍催化剂的制备方法,其特征在于:所述步骤1中水合肼与溶剂的体积比为1/30~1/3。
6.根据权利要求1所述的一种片层自组装海星状富镍碲化镍催化剂的制备方法,其特征在于:所述步骤1中的碲源为单质碲、氧化碲或亚碲酸钠中的一种。
7.根据权利要求1~6任意一项所述的一种片层自组装海星状富镍碲化镍催化剂的制备方法,其特征在于:所述步骤2中加热温度为80~200℃,反应时间为1~36h。
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