CN102534648B - 利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢的方法 - Google Patents
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Abstract
本发明涉及利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢的方法，其特征在于，采用化学腐蚀法制备超细3C-SiC纳米晶的悬浮液，将此悬浮液滴涂在导电的玻碳基片上制得超细3C-SiC纳米晶薄膜电极,将此电极用于电化学分解水制氢的反应，显示出良好的电催化活性。该催化活性产生原因在于超细3C-SiC纳米晶的表面能够通过表面自催化的过程解离水分子，形成–H和–OH分别键合在Si–Si二聚体的两端的结构，这种自催化效应能够显著降低水分解的活化势垒。将此电极用于电化学分解水制氢的反应，在低的电压下，显示出良好的电催化活性。从而实现电催化和光电化学协同作用下分解水制氢。
Description
技术领域
本发明涉及一种利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢的方法。
背景技术
氢气是一种具有很高能量密度的绿色能源载体。通过水的分解来制备氢气可以实现一个可持续的能量循环，对解决全球面临的能源和环境问题具有巨大的应用价值。由于水分解制氢在科学和技术上的重要性，长期以来人们一直在寻找高效的材料来实现电催化和光电化学分解水制氢。从物理的角度来看，固体材料的表面与水分子的相互作用应当是水分解制氢反应的推动力。然而，从分子层次上揭示材料的表面效应对氢析出反应的催化作用仍未能从实验上实现。最近，水与固体表面之间的相互作用因其在多相催化、电化学和腐蚀过程等领域的广泛应用吸引了越来越多的研究兴趣。一些研究表明，和传统观念不同，在一些固体材料表面，水分子不是简单的吸附，而是通过表面自催化过程裂解形成-H和-OH物种并键合在材料表面形成一种复合结构(G.Cicero et al.，Phys.Rev.Lett.2004，93，016102；B.Meyer et al.，Angew.Chem.Int.Ed.2004，43，6642-6645；O.Dulub et al.，Phys.Rev.Lett.2005，95，136101；G.S.Parkinson et al.，J.Am.Chem.Soc.2011，133，12650-12655.)。基于这些材料的这种表面自催化效应，开发一种先进的催化剂以实现高效率的电化学分解水制氢成为可能。
在研究水和纳米晶表面的相互作用的过程中，我们通过光致发光谱的测定发现超细3C-SiC纳米晶可以通过表面自催化效应将吸附的水分子分解，形成-H和-OH基团组成的复合结构(X.L.Wu et al，Nano Lett.2009，9，4053-4060.)。第一性原理计算表明，硅终止的3C-SiC纳米晶的表面能够解离水分子，形成-H和-OH分别键合在Si-Si二聚体的两端。这项研究为我们提供了一个基于超细3C-SiC纳米晶表面的自催化效应来降低水分解反应的势垒从而实现水分解制氢的途径。本发明所提供的利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢的方法，加深了从分子尺度对氢析出反应机理的理解，为实现可持续的和经济的氢制备技术提供了新的途径。
发明内容
本发明目的是提供一种利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢的方法，可以实现高效的电催化分解水制氢。
本发明的技术方案：一种利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢的方法，采用化学腐蚀法制备超细3C-SiC纳米颗粒的悬浮液，制得超细3C-SiC纳米晶的粒度分布为1.5～7.5nm，最多分布的粒径是3～6nm。将此悬浮液滴涂在导电的玻碳基片上制得超细3C-SiC纳米晶薄膜电极，将此电极用于电化学分解水制氢的反应，显示出良好的电催化活性。该电催化活性产生的原因是超细3C-SiC纳米晶的表面能够通过表面自催化过程解离水分子，形成-H和-OH分别键合在Si-Si二聚体的两端的结构，这种自催化效应能够显著降低水分解的活化势垒。3C-SiC纳米粒子的尺寸在激子波尔半径附近才能有明显的自催化分解水的效应，并且随着粒径的降低催化能力增强。
化学腐蚀法制备超细3C-SiC纳米晶的方法：通常情况下，约6.0克微米级的3C-SiC粉体放置于塑料烧杯作为反应物，蚀刻液为15毫升65wt％硝酸(HNO3)和45毫升40wt％氢氟酸(HF)组成，蚀刻反应温度为100～110℃，反应时间为1小时。反应后，将所得酸与粉末的混和液冷却至室温，静置数小时或离心沉淀(8000转/分钟，离心5分钟)后，倒去上层反应残余酸液。将得到的粉末用去离子水反复清洗，再将得到的粉末置于烘箱中在70℃下经数小时烘干。将烘干后的粉末放置于玻璃烧杯中，加入30毫升去离子水，超声振荡约30～60分钟。将所得产物静置数小时或离心沉淀(8000转/分钟，离心10分钟)后，取上层清液，即可得超细3C-SiC纳米晶在水中的悬浮液。透射电子显微镜表征结果表明所得纳米晶的形貌为近似球形，通过粒度分析仪测试得到粒度分布为1.5～7.5nm。
所述的超细3C-SiC纳米晶对水分解的电催化性能的测试在连接三电极体系电解池的CHI660D电化学工作站上进行。所用工作电极为超细3C-SiC纳米晶薄膜负载的玻碳基片，Ag/AgCl(3mol L-1氯化钾填充)电极和铂丝电极分别作为参比电极和对电极，0.5mol L-1的Na2SO4溶液(pH＝6.0)作为电解液。超细3C-SiC纳米晶薄膜电极的制备按如下程序进行：取15毫升上述制备的浓度为1mg mL-1的3C-SiC纳米晶的悬浮液和0.4毫升5％的Nafion溶液，超声处理30分钟左右，然后滴涂在玻碳基片上，在70℃下蒸发掉溶剂即得超细3C-SiC纳米晶薄膜电极。
新制备的3C-SiC纳米晶(颗粒平均直径为3.6纳米)薄膜电极在不同的时间连续测量其线性扫描伏安曲线。第一次扫描结果表明样品显示出非常小的开启电势。随着扫描次数的增加，开启电势也在增大(也即开启电势逐渐变负)，并最终达到一个稳定值。在化学腐蚀法制备超细3C-SiC纳米晶的过程中，SiC纳米颗粒的表面吸附了大量的H+，开启电势的增大正是由于吸附的H+的解离所致。从几次测试后稳定的极化曲线可以看出超细3C-SiC纳米晶薄膜电极比空白的玻碳电极展示出对氢析出反应的更好的电催化活性。这种电催化活性即来自于超细3C-SiC纳米晶表面的自催化效应能够降低水分解的势垒。随着纳米晶尺寸的降低(平均尺寸从3.6nm降低到3.0nm)，对氢析出反应的催化活性增加。与之形成对比的是，相同负载量的商业化的的3C-SiC纳米晶(平均尺寸为20nm)在相同条件下进行实验，测到可忽略的电流。这些结果表明，纳米晶的尺寸在对氢析出反应电催化活性有重要影响。超细3C-SiC纳米晶薄膜电极在-0.8V偏压(相对于Ag/AgCl参比电极)的电流-时间曲线趋于直线(电流值保持恒定)，表明该材料对氢析出反应的稳定性。
超细3C-SiC纳米晶薄膜电极能够加速氢析出反应的机理分析如下：当水分子扩散到3C-SiC纳米粒子硅终止表面的一个合适的解离中心，他们能自发地分裂成-H 和-OH物种并键合在材料表面的相邻的硅原子(硅二聚体)上形成一种复合结构。这种超细3C-SiC表面地自催化效应能够显著降低水解离的活化势垒。并且纳米粒子的尺寸越小，其必表面积越大，因此具有较高的催化活性。在有外加电势的条件下，当电子从电极转移到电极上时，表面上的氢原子即被还原而产生氢分子。这种通过水分解制氢的途径比传统的直接电解水制氢具有较低的活化势垒。水分子不断的在3C-SiC纳米晶薄膜电极表面吸附并解离，这种持续的动力学过程即成为高效制氢的过程。本发明提供的方法可以在室温下电催化分解水制氢，尤其是在弱酸性电解液的条件下效果最佳。
本发明所使用的3C-SiC纳米颗粒的水溶液为酸性，用NaOH溶液调节纳米颗粒水溶液至碱性(pH值为10.5)，测试结果表明这种样品不具有电催化活性。特定的表面H+的浓度对3C-SiC纳米颗粒的表面自催化效应是必须的。在碱性溶液的条件下，大量的-OH基团终止了3C-SiC纳米颗粒表面的Si悬挂键，造成纳米颗粒表面不能自发解离水分子，这种弱的自催化效应导致在碱性条件下对氢析出反应丧失电催化活性。
3C-SiC作为一种具有合适的带隙(2.24eV)和平带电势、高的熔点和耐腐蚀性的半导体材料，可以作为光阴极材料用于光电化学分解水制氢。上述超细3C-SiC纳米晶薄膜电极在500W氙灯光照的情况下表现出更好的对氢析出反应的电催花活性。超细3C-SiC纳米晶薄膜电极可以在电催花和光电化学协同作用分解水制氢中得到应用。
本发明的主要特点和优势如下：
1.本发明利用超细3C-SiC纳米晶表面自催化效应降低水分解的势垒从而实现高效电催化分解水制氢。催化分解水制氢的效果随着颗粒尺寸的降低而增强。
2.本发明所使用的3C-SiC纳米颗粒的水溶液为弱酸性或中性，在碱性下这种样品不具有电催化活性。特定的表面H+的浓度对3C-SiC纳米颗粒的表面自催化效应是必须的。在碱性溶液的条件下，大量的-OH基团终止了3C-SiC纳米颗粒表面的Si悬挂键，造成纳米颗粒表面不能自发解离水分子。
3.本发明所用的超细3C-SiC纳米晶薄膜电极可以作为光阴极材料用于光电化学分解水制氢，从而可以在电催化和光电化学协同作用分解水制氢中得到应用。
附图说明
图1.本发明所用的超细3C-SiC纳米颗粒的形貌和结构表征图。(a，b)超细3C-SiC纳米颗粒的透射电镜照片和尺寸分布图，由图可知其平均粒径为3.6nm。(c，d)平均尺寸为20nm的商业化的3C-SiC纳米颗粒的透射电镜照片和X射线衍射图谱。
图2.图1中所示的两种3C-SiC纳米颗粒的水溶液(pH＝5.5)在360nm的波长激发下的光致发光谱图。对3.6nm的超细3C-SiC纳米颗粒，除了450nm的由量子限域效应所产生的发光外，510nm处的发光峰是由于-H和-OH物种键合在纳米颗粒表面所致。这个510nm处的发光峰是确立表面自催化效应的依据。当颗粒尺寸增大以后，这个发光峰消失，表明表面的自催化效应的消失。
图3.本发明所用的电催化和光电化学分解水制氢的实验装置示意图。阴阳两级用Nafion 117的膜隔开，工作电极和参比电极用鲁金毛细管分开并相互靠近。
图4.不同尺寸的3C-SiC纳米晶薄膜电极的线性扫描伏安曲线和稳定性曲线。(a，b)本发明所用的两种不同尺寸的超细3C-SiC纳米颗粒[3.6nm(a)和3.0纳米(b)]在不同测试时间(从A至F)连续测量得到的线性扫描伏安曲线，空白的玻碳基片作为比较。(c)两种不同尺寸的超细3C-SiC纳米颗粒稳定的线性扫描伏安曲线，空白的商业化平均尺寸为20nm的3C-SiC纳米和铂片电极的数据作为比较。上述测试所用电解液为0.5mol L-1 Na2SO4溶液(pH值6.0)，扫描速度为10mV S-1。(d)超细3C-SiC纳米晶薄膜电极在-0.8V(vsAg/AgCl电极)外加偏压下的电流-时间曲线。
图5.利用超细3C-SiC纳米晶薄膜电极表面自催化效应实现电化学分解水制氢原理的示意图。纳米颗粒负载在玻碳基片上，3C-SiC纳米颗粒用硅终止的(001)面标示，水分子解离形成-H和-OH物种分别键合在Si-Si二聚体两端的结构。
图6.超细3C-SiC纳米晶薄膜电极的光电流和暗电流曲线。
具体实施方式
实施例1利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢。
取15毫升制备的浓度为1mg mL-1的3C-SiC纳米晶的悬浮液(平均粒径为3.6nm)和0.4毫升5％的Nafion溶液，超声处理30分钟左右，然后滴涂在玻碳基片上，在70℃下蒸发掉溶剂即得超细3C-SiC纳米晶薄膜电极。将此电极连接作为工作电极连接在三电极体系电化学工作站上(如附图3)。从若干次测试后稳定的极化曲线可以得到超细3C-SiC纳米晶薄膜电极比空白的玻碳电极展示出对氢析出反应的更好的电催化活性，并且该电极在-0.8V偏压(相对于Ag/AgCl参比电极)的电流-时间曲线表明该材料对氢析出反应的稳定性(附图4)。
实施例2利用超细3C-SiC纳米晶薄膜电极实现电催化和光电化学协同效应实现水分解制氢。
与实施例1中操作步骤相似，本例是通过在500W氙灯光照的情况下测试超细3C-SiC纳米晶薄膜电极对氢析出反应的光电催花性能，从而实现电催化和光电化学协同效应分解水制氢。测试结果表明，在光照的条件下，3C-SiC纳米晶薄膜电极显示出增强的电催化活性(附图6)。
Claims (2)
1.一种利用超细3C-SiC纳米晶表面自催化效应电化学分解水制氢的方法，其特征在于，采用化学腐蚀法制备超细3C-SiC纳米晶的悬浮液，将此悬浮液滴涂在导电的玻碳基片上制得超细3C-SiC纳米晶薄膜电极,将此电极用于电化学分解水制氢的反应；3C-SiC纳米晶中纳米粒子的尺寸在激子波尔半径附近即1.5～7.5 nm；3C-SiC纳米晶的悬浮液为弱酸性或中性。
2.如权利要求1所述的方法，其特征在于，3C-SiC纳米晶薄膜电极在光照的条件下通过电催化和光电化学协同效应分解水制氢。
3. 如权利要求1所述的方法，其特征在于，3C-SiC纳米晶的形貌为近似球形，粒度分布为1.5～7.5 nm；采用如下方法制备：6.0克微米级的3C-SiC粉体放置于塑料烧杯作为反应物，蚀刻液由15毫升65 wt%硝酸和45毫升40 wt%氢氟酸组成,上述蚀刻液与粉体进行蚀刻反应，温度为100～110 °C，反应时间为1小时；反应后，将蚀刻液与粉体反应所得酸液与粉末的混和液冷却至室温，静置数小时或离心沉淀后，倒去上层反应残余酸液；将得到的粉末用去离子水反复清洗，再将得到的粉末置于烘箱中在70 °C下经数小时烘干；将烘干后的粉末放置于玻璃烧杯中，加入30毫升去离子水，超声振荡30～60分钟；将所得产物静置数小时或离心沉淀后，取上层清液，即得上述规格的超细3C-SiC纳米晶在水中的悬浮液。
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