CN111530502B - 一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法 - Google Patents
一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种ZnTe‑Mo/Mg‑MOF光阴极材料的制备方法，属于光电催化技术领域。所述的复合光电极由p型ZnTe半导体和Mo/Mg双金属MOF组成，其中ZnTe通过热蒸发沉积和液相反应法合成，可以有效吸收可见光，而Mo/Mg‑MOF能够有效捕获和活化CO2，二者协同作用，显著提高ZnTe还原CO2的电流密度，降低反应起始电位。本发明所述复合光电极材料制备过程简单，对CO2还原具有优异的活性和选择性，在光电催化领域具有较好的应用前景。
Description
技术领域
本发明属于光电催化技术领域，具体涉及一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，可以实现CO2分子的有效捕获和活化，降低CO2还原的反应能垒，有效提升ZnTe光电催化还原CO2为CO的活性和选择性。
背景技术
能源短缺和温室效应是当今人类面临的难题，减少CO2排放，将其转变为碳氢燃料，已成为各国科学家的重点研究方向。目前，人工CO2转化的方法主要有高温催化加氢法、电催化还原法、光催化转化法和光电催化方法等，其中光催化载流子分离效率较低，电催化过电位较高，而光电催化集合光催化的低能耗与电催化的高能效等优势，有利于降低反应的过电势，促进光生载流子和产物的分离，是一种有效的CO2转化方法。
ZnTe的导带电位为-1.63V vs.NHE，比大多数碳基产物的电势更负，有利于克服CO2活化的热力学势垒，且ZnTe的带隙窄(2.26eV)、载流子迁移率高，受到越来越多关注。然而，和大多数无机半导体类似，光激发ZnTe产生的光生电子和空穴复合速率极快，导致单一ZnTe光电催化还原CO2的活性较低。此外，在含水溶液中，质子还原和CO2还原竞争激烈，且质子还原在动力学上更快，导致ZnTe光电催化还原CO2的选择性也较低。
针对上述问题，人们急切希望开发新型ZnTe基光阴极材料，以促进CO2高活性和高选择性转化。受植物光合作用启发，自然界中绿色植物的叶子能够通过卡尔文循环中的1,5-二磷酸核酮糖羧化酶(RuBisCo)固定和活化CO2，随后质子耦合电子转移将CO2转化为碳氢化合物。而金属有机框架材料MOFs具有丰富的孔道结构、高密度的配位不饱和金属位点，以及优异的CO2吸附性能，将Mo/Mg双金属MOF引入到ZnTe半导体界面，有望构筑具有优异的CO2固定和活化功能的“人工叶子”，从而实现CO2还原仿生界面的构筑。本发明发现Mo/Mg双金属MOF中的Mg位点对水溶液中的CO2分子具有优异的吸附能力，而Mo位点可以催化CO2还原，定向转化为CO，这对CO2的资源化利用具有重要的科学意义和实际应用价值。
发明内容
本发明针对现有技术的不足，提供一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法。其目的在于利用ZnTe半导体和Mo/Mg-MOF材料之间的电荷转移作用，协同提高ZnTe材料光电催化CO2还原的活性和选择性。本发明的目的通过以下技术方案实现：
本发明提供一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法,所述方法由以下步骤组成：
1)以水、乙醇和丙酮清洗FTO玻璃，N2吹干，备用。以TeO2作为靶材，在室温下通过热蒸发法将TeO2粉末蒸发到FTO基板上，即得TeO2薄膜；
2)配制乙酸锌和硼氢化钠的混合水溶液，将上述TeO2薄膜放置于该溶液中，90℃水浴下反应1-5小时，即得ZnTe薄膜；
3)配制乙酸钼、乙酸镁的前驱体水溶液，再加入合成金属有机框架材料(MOF)所需的有机配体，搅拌混合均匀，转入水热反应釜中。然后将ZnTe薄膜斜插入反应釜内胆中，薄膜导电面朝下，水热反应一定时间，待反应釜冷却后，取出薄膜样品，水洗、乙醇洗。最后，将获得的样品在N2气氛下煅烧一定时间，以除去MOF孔道中的溶剂分子，即得ZnTe-Mo/Mg-MOF光电极材料。
优选地，步骤1所述热蒸发的沉积速率为0.1-0.5nm s-1。
优选地，步骤2所述乙酸锌和硼氢化钠的摩尔比为1:1-1:3。
优选地，步骤3所述乙酸钼和乙酸镁的摩尔比为1:1-1:5。
优选地，步骤3所述有机配体为芘基羧酸配体或2,5-二羟基对苯二甲酸。
优选地，步骤3所述水热温度为180-200℃，水热时间为15-20h。
优选地，步骤3所述N2气氛下煅烧温度为250℃，煅烧时间为9-15h。
本发明的有益效果：本发明使用热蒸发法沉积制备TeO2薄膜，随后采用液相还原法将TeO2转化为ZnTe，之后采用水热法将Mo/Mg-MOF负载在ZnTe薄膜载体上，整个制备工艺简单，可实现批量化生产。且所制备的ZnTe-Mo/Mg-MOF复合光阴极材料光电催化性能优异，可在高电流密度下将CO2定向转化为CO，且该反应的法拉第效率高，反应过电位低，可以有效利用太阳能实现低电位下CO2转化为C1化合物，具有重要的应用价值。
附图说明
图1为实施例三中制备的ZnTe-Mo/Mg-MOF和ZnTe电极的线性扫描伏安曲线图；
图2为实施例四中制备的ZnTe-Mo/Mg-MOF和ZnTe电极在模拟太阳光照射下的H2和CO生成量，电位：-0.4V，光照时间为4小时。
具体实施方式
为了更好的理解本发明，下面结合实施例和附图进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例一
一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，具体步骤如下：将FTO导电玻璃置于超声清洗器中分别经水洗、乙醇洗和丙酮洗，最后用高纯N2吹干洗净的FTO玻璃，待用。然后在室温下通过热蒸发法将TeO2粉末蒸发到FTO基板上，将TeO2靶材放置于钽舟中，并将反应室内的压力抽真空至4.5×10-5Pa，在外加电流的作用下TeO2靶材以0.2nm s-1的沉积速率蒸发，获得TeO2薄膜；随后，配制0.5mol/L的乙酸锌和0.5mol/L硼氢化钠的水溶液，将TeO2薄膜放置于该溶液中，90℃水浴下反应2小时，即得ZnTe薄膜；称200mg 2,5-二羟基对苯二甲酸、100mg乙酸钼和200mg乙酸镁，放入玻璃烧杯中，加入30mL去离子水，搅拌溶解。然后将此溶液转入50mL反应釜中，随后在190℃烘箱中反应15小时。反应结束后，反应釜自然冷却至室温，然后采用水和乙醇清洗薄膜样品。最后将该材料在N2惰性气氛下于250℃活化9小时，以除去MOF孔道中的溶剂分子，即得ZnTe-Mo/Mg-MOF光电极材料。
实施例二
一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，具体步骤如下：将FTO导电玻璃置于超声清洗器中分别经水洗、乙醇洗和丙酮洗，最后用高纯N2吹干洗净的FTO玻璃，待用。然后在室温下通过热蒸发法将TeO2粉末蒸发到FTO基板上，将TeO2靶材放置于钽舟中，并将反应室内的压力抽真空至4.5×10-5Pa，在外加电流的作用下TeO2靶材以0.3nm s-1的沉积速率蒸发，获得TeO2薄膜；随后，配制0.8mol/L的乙酸锌和1mol/L硼氢化钠的水溶液，将TeO2薄膜放置于该溶液中，90℃水浴下反应3小时，即得ZnTe薄膜；称100mg 1,3,6,8-(4-羧基苯基)芘、100mg乙酸钼和150mg乙酸镁，放入玻璃烧杯中，加入30mL去离子水，搅拌溶解。然后将此溶液转入50mL反应釜中，随后在195℃烘箱中反应16小时。反应结束后，反应釜自然冷却至室温，然后采用水和乙醇清洗薄膜样品。最后将该材料在N2惰性气氛下于250℃活化10小时，以除去MOF孔道中的溶剂分子，即得ZnTe-Mo/Mg-MOF光电极材料。
实施例三
一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，具体步骤如下：将FTO导电玻璃置于超声清洗器中分别经水洗、乙醇洗和丙酮洗，最后用高纯N2吹干洗净的FTO玻璃，待用。然后在室温下通过热蒸发法将TeO2粉末蒸发到FTO基板上，将TeO2靶材放置于钽舟中，并将反应室内的压力抽真空至4.5×10-5Pa，在外加电流的作用下TeO2靶材以0.1nm s-1的沉积速率蒸发，获得TeO2薄膜；随后，配制0.25mol/L的乙酸锌和0.5mol/L硼氢化钠的水溶液，将TeO2薄膜放置于该溶液中，90℃水浴下反应4小时，即得ZnTe薄膜；称120mg 2,5-二羟基对苯二甲酸、150mg乙酸钼和180mg乙酸镁，放入玻璃烧杯中，加入30mL去离子水，搅拌溶解。然后将此溶液转入50mL反应釜中，随后在190℃烘箱中反应15小时。反应结束后，反应釜自然冷却至室温，然后采用水和乙醇清洗薄膜样品。最后将该材料在N2惰性气氛下于250℃活化10小时，以除去MOF孔道中的溶剂分子，即得ZnTe-Mo/Mg-MOF光电极材料。
将上述ZnTe-Mo/Mg-MOF光电极材料放入光电化学反应器内，与铂片对电极和饱和甘汞参比电极组装成三电极体系，选用0.5M KHCO3作为电解质溶液，采用上海辰华CHI660E电化学工作站测试复合电极在模拟太阳光照下的电流密度。光电流测试前，往电解质溶液中鼓CO2半个小时，使溶液中的氧气排尽，CO2浓度达到饱和。图1为本实施例制备的ZnTe-Mo/Mg-MOF光电极和ZnTe薄膜电极的线性扫描伏安法图，扫描速度为20mV/s。由图可知，随着电极电位逐渐负移，光电流密度逐渐增加，说明在在光电协同催化作用下，电极的载流子分离效率增加。此外，Mo/Mg-MOF负载后，ZnTe的光电流密度显著增强，且起始电位正移，说明Mo/Mg-MOF能够提高ZnTe光电催化CO2还原活性。
实施例四
一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，具体步骤如下：将FTO导电玻璃置于超声清洗器中分别经水洗、乙醇洗和丙酮洗，最后用高纯N2吹干洗净的FTO玻璃，待用。然后在室温下通过热蒸发法将TeO2粉末蒸发到FTO基板上，将TeO2靶材放置于钽舟中，并将反应室内的压力抽真空至4.5×10-5Pa，在外加电流的作用下TeO2靶材以0.1nm s-1的沉积速率蒸发，获得TeO2薄膜；随后，配制1.25mol/L的乙酸锌和1.5mol/L硼氢化钠的水溶液，将TeO2薄膜放置于该溶液中，90℃水浴下反应3小时，即得ZnTe薄膜；称150mg 1,3,6,8-(4-羧基苯基)芘、50mg乙酸钼和80mg乙酸镁，放入玻璃烧杯中，加入30mL去离子水，搅拌溶解。然后将此溶液转入50mL反应釜中，随后在200℃烘箱中反应15小时。反应结束后，反应釜自然冷却至室温，然后采用水和乙醇清洗薄膜样品。最后将该材料在N2惰性气氛下于250℃活化12小时，以除去MOF孔道中的溶剂分子，即得ZnTe-Mo/Mg-MOF光电极材料。
图2为本实施例制备的ZnTe-Mo/Mg-MOF电极和ZnTe薄膜电极在-0.4V偏压作用下光照4小时生成的H2和CO柱图。由图可知，ZnTe光电催化CO2活性较差，碳基产物极少，而产物以H2为主。Mo/Mg-MOF负载后，ZnTe的产物以CO为主，H2析出活性得到有效抑制，且CO产量大幅增加，证实Mo/Mg-MOF能提高ZnTe光电催化活性和选择性。
Claims (7)
1.一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，其特征在于由以下步骤组成：
1)以水、乙醇和丙酮清洗FTO玻璃，N2吹干，备用，以TeO2作为靶材，在室温下通过热蒸发法将TeO2粉末蒸发到FTO基板上，即得TeO2薄膜；
2)配制乙酸锌和硼氢化钠的混合水溶液，将上述TeO2薄膜放置于该溶液中，90℃水浴下反应1-5小时，即得ZnTe薄膜；
3)配制乙酸钼、乙酸镁的前驱体水溶液，再加入合成金属有机框架材料(MOF)所需的有机配体，搅拌混合均匀，转入水热反应釜中，然后将ZnTe薄膜斜插入反应釜内胆中，薄膜导电面朝下，水热反应一定时间，待反应釜冷却后，取出薄膜样品，水洗、乙醇洗，最后，将获得的样品在N2气氛下煅烧一定时间，以除去MOF孔道中的溶剂分子，即得ZnTe-Mo/Mg-MOF光电极材料。
2.根据权利要求1所述的一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，其特征在于，步骤1所述热蒸发的沉积速率为0.1-0.5nm s-1。
3.根据权利要求1所述的一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，其特征在于，步骤2所述乙酸锌和硼氢化钠的摩尔比为1:1-1:3。
4.根据权利要求1所述的一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，其特征在于，步骤3所述乙酸钼和乙酸镁的摩尔比为1:1-1:5。
5.根据权利要求1所述的一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，其特征在于，步骤3所述有机配体为2,5-二羟基对苯二甲酸。
6.根据权利要求1所述的一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，其特征在于，步骤3所述水热温度为180-200℃，水热时间为15-20h。
7.根据权利要求1所述的一种ZnTe-Mo/Mg-MOF光阴极材料的制备方法，其特征在于，步骤3所述N2气氛下煅烧温度为250℃，煅烧时间为9-15h。
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