CN114959778B - 一种碳布负载的多酸衍生铜钼硫化物的制备 - Google Patents
一种碳布负载的多酸衍生铜钼硫化物的制备 Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000004744 fabric Substances 0.000 title claims abstract description 40
- OIGPMFVSGDDYHS-UHFFFAOYSA-N copper sulfanylidenemolybdenum Chemical compound [S].[Cu].[Mo] OIGPMFVSGDDYHS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
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- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 13
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- 229910021641 deionized water Inorganic materials 0.000 claims description 12
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
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- 229910017489 Cu I Inorganic materials 0.000 claims 1
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
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Abstract
本发明涉及电催化析氢领域一种碳布负载的异金属硫化物的制备及其应用。本发的目的是解决现有技术合成高性能电催化剂的原材料储备稀少、析氢反应过电位较高、造价昂贵的问题。本专利设计与研制了一种碳布负载的异金属硫化物材料Cu2S‑MoS2。所采用的方法:以Keggin型多酸磷钼十二、硫脲和碳布为原料,采用一步水热合成方法,制备的碳布负载的多酸衍生铜钼硫化物可适用于碱性电解液中的电催化析氢反应且具有低析氢过电位和高催化活性。
Description
技术领域
本发明涉及电催化析氢领域。
背景技术
由于化石燃料的迅速枯竭和全球环境的恶化,探索可持续和清洁能源来替代枯竭的化石燃料显得极其迫切。许多研究人员专注于开发风能和太阳能等绿色、无污染的清洁能源,但这些新能源的应用受到其空间限制和时间不稳定性的严重限制。电催化制氢技术由于其清洁和生产可持续的优点而吸引了各界极大的兴趣,氢能是化石燃料的潜在替代能源。贵金属材料(例如,铂和贵金属氧化物)通常被用作最先进的电催化剂,用于电催化产氧反应。然而,铂族材料的高成本和稀缺性限制了其大规模和可持续的应用。除了开发无金属催化剂外,用更便宜的过渡金属元素进行合金化是降低成本的一种策略。多酸具有良好的氧化还原能力,可以可逆地接受和释放一个或多个电子。而电化学反应正是通过电子转移发生,所以这为其作为HER催化剂提供了可能。并且多酸合成方法简单、成本低廉、结构缤纷多样、具有氧化还原活性高的金属元素,多酸可以通过共价键与有机体系结合为多酸基无机-有机杂化化合物,还可以取代或掺杂其他元素,形成的杂多酸纳米团簇,这样可以对多酸的电化学等性质进行一定的调节。并且,通过一些手段使多酸与其他物质结合为复合材料也是调节多酸本身性能的手段。先前研究表明双金属基复合材料的电催化性能更胜一筹。因此,以多酸为前驱体制备高活性、高稳定性和导电性的双金属基复合材料是一项有前途且有意义的工作。
发明内容
为了克服上述现有电催化析氢催化剂比表面积低,价格昂贵以及多酸作为原料稳定性差、导电性差、等不足,本发明提供了一种制备简单、价格低廉的方法且制备出的一种碳布负载的多酸配合物衍生异金属硫化物作为电催化析氢催化剂材料具有较高的电催化性能和良好的稳定性等优点。
本发明的目的是这样实现的:
一种碳布负载的多酸衍生铜钼硫化物的制备,包括以下步骤:
(1)将碳布裁剪成约1x1.5 cm2的长方形方块,依次用丙酮、乙醇和去离子水对其进行超声处理30min,然后再将碳布浸泡在浓硝酸中,转移到水热反应釜中,100℃恒温1~2h,降至室温后,回收硝酸待下次重复使用,再用去离子水反复冲洗碳布,放入烘箱中80℃烘干过夜备用。
(2)将0.09g的磷钼十二多酸,0.045g的Cu(NO3)2·3H2O,0.015g的有机配体2,2'-bipy 和0.01g的草酸,加入10mL去离子水,常温搅拌3h。配制0.5M HNO3将上述溶液pH 值调节至约2.43,转入反应釜中,在160℃鼓风干燥箱中恒温反应96h,以10℃h-1的程序降温速度,降温至室温后,得到晶体,挑选干燥。
(3)称取0.1g晶体将其放入研钵中研磨成粉末状,加入0.2g的硫脲,一片已处理过的碳布,加入10mL去离子水,超声处理1h,转入反应釜中,在200℃鼓风干燥箱中高温反应,待室温后冲洗数次,然后在60℃干燥箱中干燥,即得到碳布负载的异金属硫化物Cu2S-MoS2,在碳布表面均匀覆盖。
上述的碳布负载的多酸衍生铜钼硫化物的应用,主要是在电催化分解水析氢方面。
上述应用方法如下:以1.0摩尔每升氢氧化钾水溶液作为电解液溶液,所述碳布负载的铜钼硫化物材料Cu2S-MoS2作为工作电极,以饱和甘汞电极为参比电极,碳棒电极作为对电极,如此搭建三电极体系。在碱性电解质溶液中,当过电位为109mV时,电流密度为10mAcm-2,并可保持稳定工作状态24个小时。
与现有技术相比,本发明具有如下特点:
发明通过采用Keggin型多酸为前驱体提供稳定的双金属源,它不仅有效突破了以往以简单钼酸钠和金属盐为主要原料的传统制备双金属硫化物技术线路中反应原料混合不均匀、彼此分离、反应不同步、产物形貌不一、容易团聚等技术瓶颈,有效的克服了在水热过程中游离金属盐具有不同成核速率的缺点。而且实现了定向制备高分散的双金属硫化物的目的。并且两种过渡金属硫化物发挥两者之间的协同效应促进电催化性能。这种材料在作为电催化析氢催化剂时,结果表明其具有良好的析氢性能和较低的过电位,在碱性电解质溶液中,当过电位为109mV时,电流密度为10mAcm-2,并可保持稳定工作状态24 个小时。本发明所制备的晶态多酸配位聚合物可以提供精确比例的异金属源,在硫脲作用下,形成了纳米片结构材料,尤其是Cu2S的掺杂,实现了对MoS2纳米片边缘暴露活性位点的调控,增大了表面活性位点数量,并且复合材料中MoS2和Cu2S之间极大的电子的相互作用进一步提高了材料的析氢性能,因而制备出所需的复合电极材料。
附图说明
图1为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物在碱性电解质溶液中不同时间下的析氢极化曲线。
图2为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物的XRD谱图。
图3为本发明实施例1所制备的晶态多酸配位聚合物的红外测试谱图。
图4为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物在不同反应时间下的塔菲尔斜率图。
图5为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物在24h的电流-密度扫速图(插图为循环伏安图)。
图6为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物在不同尺寸下的扫描电镜图。
图7为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物的制备流程。
具体实施方式
下面结合附图和实施例对本发明进行详细的说明。
实施例1,一种碳布负载的多酸衍生铜钼硫化物,包括如下制备步骤:
(1)将碳布裁剪成约1x1.5 cm2的长方形方块,用丙酮、乙醇和去离子水对其各进行超声处理30min,然后再将碳布浸泡在浓硝酸中,转移到水热反应釜中,100℃恒温1~2h,降至室温后,回收硝酸待下次重复使用,再用去离子水反复冲洗碳布,放入烘箱中80℃烘干过夜备用。其中使用丙酮是为了除去表面的杂质和不溶物,乙醇是为了除去有机物杂质,水是为了去除残留的丙酮和乙醇。
(2)将0.09g的磷钼十二多酸,0.045g的Cu(NO3)2·3H2O,0.015g的有机配体 2,2'-bipy和0.01g的草酸,加入10mL去离子水,常温搅拌3h。配制0.5M HNO3将上述溶液pH值调节至约2.43,转入反应釜中,在160℃鼓风干燥箱中恒温反应96h,以10℃ h-1的程序降温速度,降温至室温后,得到晶体,挑选干燥。
制备的一种磷钼酸盐构筑的多酸基铜金属有机杂化材料的X-单晶衍射结构解析数据见表1,所用仪器为布鲁克公司的ApexII单晶衍射仪;
表1
aR1=∑║Fo│─│Fc║/∑│Fo│,bwR2=∑[w(Fo 2─Fc 2)2]/∑[w(Fo 2)2]1/2
(3)称取0.1g晶体将其放入研钵中研磨成粉末状,加入0.2g的硫脲,一片已处理过的碳布,加入10mL去离子水,超声处理1h,转入反应釜中,在200℃鼓风干燥箱中高温反应,待室温后冲洗数次,然后在60℃干燥箱中干燥,即得到碳布负载的异金属硫化物Cu2S-MoS2,在碳布表面均匀覆盖。
下面结合附图及实施例,对本发明做进一步的说明:
如图1所示为一种碳布负载的多酸衍生铜钼硫化物在碱性电解质溶液中的析氢极化曲线。可以观察到当电流密度为10mAcm-2时,电极材料过电位为109mV。
如图2所示为一种碳布负载的多酸衍生钴钼硫化物的XRD谱图,从图中可以观察到目标材料出现了不同的特征峰,与Cu2S和MoS2的标准比色卡进行对比,可以看到MoS2和Cu2S的衍射峰出现在目标材料的PXRD图谱上。2θ为39.5°、49.7°处的衍射峰分别对应了 2H-MoS2的(103)、(105)晶面(JCPDS No.37-1492)。目标材料在2θ为31.8°、35.4°、 45.7°处的衍射峰分别对应Cu2S的(200)、(210)、(220)晶面(JCPDS No.46-1195)。如图3所示为晶态多酸配位聚合物的红外测试谱图,其中600-1000cm-1范围内的特征峰归属于PMo12阴离子簇的伸缩振动峰,1100-1700cm-1归属于有机配体2,2'-bipy的特征峰。因此,红外测试结果可以证明晶态多酸配位聚合物中存在多酸和配体。
如图4为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物在不同反应时间下的塔菲尔斜率图。电极材料的Tafel斜率约为109mV·dec-1。
图5为本发明实施例1所制备的一种碳布负载的多酸衍生铜钼硫化物在24h的电流-密度扫速图(插图为循环伏安图)。
如图6所示为一种碳布负载的多酸衍生铜钼硫化物在不同尺寸下的扫描电镜图,可以观察到碳布表面覆盖着均匀的MoS2和Cu2S的纳米片结构。
综上,本实施例运用一步水热合成法,利用磷钼酸,金属铜盐以及配体2,2-联吡啶,硫脲成功合成出具有具有电催化分解水制氢气效果的多酸基晶体材料。
Claims (3)
1.一种碳布负载的多酸衍生铜钼硫化物,其制备方法包括以下步骤:
(1)将0.09g的磷钼十二多酸,0.045g的Cu(NO3)2·3H2O,0.015g的有机配体2,2'-联吡啶和0.01g的草酸,加入10mL去离子水,常温搅拌3h;配制0.5M HNO3将上述溶液pH值调节至2.43,转入反应釜中,在160℃鼓风干燥箱中恒温反应96h,以10℃h-1的程序降温速度,降温至室温后,得到晶体[H42{CuI(bipy)}6(Mo6O22)](H4PMo6O20)2·H2O,其中,晶系为单斜晶系;空间群为P21/c;单胞参数为α=90°,β=90.1°,γ=90°, z=2;
(2)将碳布裁剪成1x1.5 cm2的长方形方块,完全浸泡在丙酮、乙醇和去离子水中对其依次进行超声处理30min,然后将处理完的碳布在60℃烘箱中烘干;再将其完全浸泡在浓硝酸中,转移到水热反应釜中100℃恒温1~2h,直到降至室温后,回收硝酸待下次重复使用,再用去离子水反复冲洗碳布,放入烘箱中80℃烘干过夜备用;
(3)称取0.1g晶体将其放入研钵中研磨成粉末状,加入0.2g的硫脲,一片已处理过的碳布,加入10mL去离子水,超声处理1h,转入反应釜中,在200℃鼓风干燥箱中高温反应,待室温后冲洗数次,然后在60℃干燥箱中干燥,即得到碳布负载的异金属硫化物Cu2S-MoS2,在碳布表面均匀覆盖。
2.权利要求1所述的一种碳布负载的多酸衍生铜钼硫化物的应用,其特征在于,应用于电催化分解水制氢领域。
3.根据权利要求2所述的应用,其特征在于,应用方法如下:以1.0摩尔每升氢氧化钾水溶液为电解液溶液,所述碳布负载的多酸衍生铜钼硫化物作为工作电极,以饱和甘汞电极为参比电极,碳棒电极作为对电极,在碱性电解质溶液中,当过电位为109mV时,电流密度为10mAcm-2,并在工作状态24个小时之后仍然保持稳定。
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