CN114956265A - 一种自发光的光电协同催化电极及其应用 - Google Patents
一种自发光的光电协同催化电极及其应用 Download PDFInfo
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Abstract
本发明公开了一种自发光的光电协同催化电极，其包括基底、外延层、n型半导体材料层、p型半导体材料层、催化材料层；本发明电极首先制备基底上制备外延层，外延层上制备p或n型半导体材料层，后在其表面生长一定量的n或p型半导体材料，两种材料接触形成p‑n结；最后在p‑n结层上制备一层过渡金属氧化物，能有效的耦合光电催化效应，提升电极的催化反应性能，本发明电极适用于各种复杂环境中的光电催化反应。
Description
技术领域
本发明涉及水污染处理领域，具体涉及一种自发光的光电协同催化电极及其应用。
背景技术
光电催化反应以其二次污染少、成本低、工艺简单等特点著称，近年有大量研究将半导体材料应用于光电催化领域，研究报道了大量的可见光光催化材料，但其在实际应用时存在困难。常规光催化材料应用时需设置外加光源且应用环境中因传播介质导致大部分的光无法透过，大部分的光在传播过程中被吸收尤其是短波段部分几乎无法达到催化剂表面激发其催化活性，导致光电催化在水处理、尾气净化、电化学合成等领域大规模应用受限，如何激发催化剂在复杂环境中尤其是弱光无光环境中光电协同的催化性能成为其大规模应用的瓶颈问题。
发明内容
针对现有技术不足，本发明提供了一种用于弱光源或无光源环境中运行稳定、高效光电催化反应的自发光电极。
本发明自发光的光电协同催化电极包括基底、外延层、n型半导体材料层、p型半导体材料层、催化材料层，当电极为阳电极时，基底上覆盖一层厚度3~5μm外延层，厚度1~3μm的p型半导体材料层设置在外延层上，厚度1~3μm的n型半导体材料层设置在p型半导体材料层上，n型半导体材料层是由若干条间距相等的条块组成，催化材料层设置在n型半导体材料层和p型半导体材料层上，厚度为1~2μm；
当电极为阴电极时，基底上覆盖一层厚度3~5μm的外延层，厚度1~3μm的n型半导体材料层设置在外延层上，厚度为1~3μm p型半导体材料层设置在n型半导体材料层上，p型半导体材料层是由若干条间距相等的条块组成，催化材料层设置在p型半导体材料层和n型半导体材料层上，厚度为1~2μm。
所述基底为蓝宝石（Al2O3）、SiC、聚二甲基硅氧烷（PDMS）、Si中的一种。
所述外延层的材料是选择n型半导体材料层或p型半导体材料层中原子序数最高的两种元素制备而成。
所述n型半导体材料是在Ⅲ族元素和Ⅴ族元素中掺入O、S、Se、Te、C、Si、Ge中一种或几种制得，O、S、Se、Te、C、Si、Ge的掺入量为n型半导体材料总摩尔量的10-9-1%；或n型半导体材料是在Ⅱ族元素和Ⅵ族元素中掺入Cl、Br、I中一种或几种制得，Cl、Br、I的掺入量为n型半导体材料总摩尔量的10-9-1%；或n型半导体材料是在Ⅱ族元素和Ⅵ族元素中掺入B、Al、Ga、In中一种或几种制得， B、Al、Ga、In中一种或几种的掺入量为n型半导体材料总摩尔量的10-9-1%。
所述p型半导体材料在Ⅲ族元素和Ⅴ族元素中掺入Zn、Be、Mg、Cd中一种或几种制得，Zn、Be、Mg、Cd中一种或几种的掺入量为p型半导体材料总摩尔量的10-9-1%；或p型半导体材料是在Ⅱ族元素和Ⅵ族元素中掺入Li、Na、K中一种或几种制得，Li、Na、K中一种或几种的掺入量为p型半导体材料总摩尔量的10-9-1%；或p型半导体材料是在Ⅱ族元素和Ⅵ族元素中掺入N、P、As、Sb、Bi中一种或几种制得，N、P、As、Sb、Bi中一种或几种的掺入量为p型半导体材料总摩尔量的10-9-1%。
所述Ⅲ族元素为B、Al、Ga、In中的一种或几种，Ⅴ族元素为N、P、As、Sb、Bi中的一种或几种，Ⅱ族元素为Zn、Mg、Cd、Be中的一种或几种，Ⅵ族元素为O、S、Se、Te中的一种或几种。
n型半导体材料或p型半导体材料中所有元素加权平均原子序Z≤40。
所述催化材料层由d区元素、d区元素的氧化物中的一种或几种组成；或先由d区元素、d区元素的氧化物中的一种或几种形成底层，再在底层上形成表层，且底层元素的序数比表层元素序数高；例如铁锰合金表层铁为底层；氧化铁氧化铜混合形成表层氧化铜为底层。
本发明另一目的是将上述自发光的光电协同催化电极应用在废水处理、电化学合成、电化学检测中。
本发明中的半导体材料通过磁控溅射、分子束外延（MBE）、脉冲激光沉积、金属有机化合物气相沉积（MOCVD）等方法制备，催化材料层由水热法、凝胶法、电沉积法制备。
本发明电极是首先制备基底上制备外延层，然后外延层上制备p或n型半导体材料层，后在其表面生长一定量的n或p型半导体材料，两种材料接触形成p-n结；最后在p-n结层上制备一层过渡金属氧化物，能有效的耦合光电催化效应，提升电极的催化反应性能，该法制备工艺简单，适用于各种复杂环境中的光电催化反应。
本发明的有益效果在于：
（1）以p-n型异质结为基础的电极材料有着高电荷分离效率及高电荷转移速率的优点，体现为反应催化效率高于普通电极；
（2）相比于传统光催化材料、光电催化材料应用场景更加广泛，本发明提出在传统光催化材料上制备发光材料的电极，可在复杂环境中进行光电催化反应。
附图说明
图1为实施例1中自发光的光电协同催化电极用于降解有机物的结果示意图；
图2为实施例2自发光的光电协同催化电极用于CO2电化学还原结果示意图；
图3为实施例3中自发光的光电协同催化电极同时检测NOX、SO2的线性伏安图；
图4为实施例3中电流大小与气体浓度的校准图。
具体实施方式
下面结合具体实施方式对本发明进行详细说明，但本发明保护范围不局限于所述内容；实施例中方法如无特殊说明均为常规方法。
实施例1：本自发光的光电协同催化电极及用于废水中有机物降解
选用Al、N、P制备三元半导体材料（AlN0.6P0.4），采用金属有机化学气相沉积法制备，三甲基铝提供Al源，氨气提供N源，磷化氢提供P源，硅烷提供Si源，双环戊二烯基镁提供Mg源；本实施例中以Al2O3为基底、AlP为外延层、p型半导体材料层为AlNP掺Mg、n型半导体材料层为AlNP掺Si；催化材料层为银-氧化钴；
阳电极制备过程如下：
1、依次使用丙酮、无水乙醇、去离子水超声清洗Al2O3基底各5min，去除基底表面的污染物；
2、反应系统内压力全程保证低于10-2Pa，将Al2O3基底置于反应腔中，调节温度至1000℃，将磷化氢和三甲基铝加热后以气体的形式通入反应器中，磷化氢:三甲基铝的体积比为120:1，在基底上制备厚度3μm 的AlP外延层；
3、在950℃下，再通入气体NH3、气体双环戊二烯基镁，并控制NH3:PH3: 三甲基铝的体积比为72:48:1，双环戊二烯基镁的气量为总气量的0.3%，在AlP外延层上制备厚度2μm的p型半导体材料层；
4、准备与步骤3中材料大小相同，厚度为2μm的带条形孔、孔间距3mm的钛片，并覆盖于步骤3的p型半导体材料层表面，在1000℃下，控制NH3:PH3:三甲基铝气体的体积比为72:48:1，同时通入气体硅烷，硅烷气量是总气量的0.4%，在p型半导体材料层上制得间距3mm、厚度2μm 的条块状n型半导体材料层，去掉钛片后置于去离子水中保存；
5、配制含0.1mol/L硝酸银、0.02mol/L硝酸钴、0.01mol/L硼酸的电解液，将步骤4制得的材料置于电解液中作为工作极，铂电极和饱和甘汞电极分别作为对电极与参比电极，在-0.5V电位下电沉积30min，清洗电极后置于空气中在200℃条件下氧化2h，在n型半导体材料表层及n型半导体材料间隙中的p型半导体材料表层形成厚度1μm的银-氧化钴催化材料层，制得阳电极；
采用单室电解池，双电极体系，上述方法制得的电极为阳电极，导线与p型半导体材料接触，钛板为阴极；设计正交实验选出最佳电流密度为15.2mA/cm2，以1000mg/L浓度的焦化废水为降解对象，30min内去除率82%，结果见图1。
实施例2：本自发光的光电协同催化电极及用于CO2电化学还原
选用Zn、S、O制备三元n型半导体（ZnO0.7S0.3），n型半导体材料层的材料为ZnOS掺Ga，p型半导体材料层的材料为ZnOS掺N，采用分子束外延技术制备，Si为基底，原材料纯度均为5N，ZnS为外延层，催化材料层为铱铁合金；
阴电极过程如下：
1、依次使用丙酮、无水乙醇、去离子水超声清洗Si衬底各5min，去除基底表面的污染物；
2、将衬底放入分子束外延系统，加热至400℃，全程维持仪器内部真空度低于10- 8Pa，加热Zn与S至两种束流源的等效压强分别为6×10-9Pa和1.8×10-8Pa，升温至780℃时打开Zn与S束流源挡板在基底上生长厚度4μm的ZnS外延层；
3、开启O源与Ga源加热至等效压强为4.2×10-8Pa和2×10-10Pa，在830℃下，打开O与Ga源束流挡板在外延层上生长厚度1.2μm的Ga掺杂ZnOS层（n型半导体材料层）；
4、准备与步骤3中材料大小相同，厚度为1.2μm的带条形孔、孔间距2mm的钛片，并覆盖于步骤3的n型半导体材料层表面，开启Zn源、S源、N源与O源加热至等效压强分别为6×10-9Pa、1.8×10-8Pa、1×10-9Pa和4.2×10-8Pa，在800℃下，打开挡板在n型半导体材料层上制得间距2mm，厚度2.1μm的条块状p型半导体材料层，去掉钛片后置于去离子水中保存；
5、依次用丙酮、无水乙醇、去离子水清洗步骤4中制得的材料后，配制含有0.12mol/L的氯化铱、0.02mol/L的氯化铁、0.01mol/L硼酸的电解液，将步骤4制得的材料置于电解液中作为工作极，铂电极和饱和甘汞电极分别作为对电极与参比电极，在-0.7V电位下沉积25min，在p型半导体材料表层及p型半导体材料间隙中的n型半导体材料表层形成厚度2μm的铱铁合金层，制得阴电极；
采用三电极体系，上述方法制得的电极为工作电极（导线与n型半导体材料连接），饱和甘汞电极为参比电极，银丝作为对电极，以离子液体[HMIm]BF4作为电解质，通入CO2使其吸收量达到饱和；通过CV法得出还原电位后，采用恒电位计时法在还原峰电位位置进行CO2还原，1小时反应结束，期间可得到CO、CH4等气体产物，结果见图2。
实施例3：本自发光的光电协同催化电极及用于废气NOX、SO2检测
选用Ga、N制备二半导体材料（GaN），采用金属有机化学气相沉积法制备，三甲基镓提供Ga源，氨气提供N源，锗烷提供Ge源，二乙基锌提供Zn源；本实施例中以Si为基底、GaN为外延层、p型半导体材料层为GaN掺Zn 、n型半导体材料层为GaN掺Ge；催化层材料为铅铜合金。
阳电极制备过程如下：
1、去除样品表面的有机物等杂质，依次使用丙酮、无水乙醇、去离子水超声清洗Si衬底各5min；
2、反应系统内压力全程保证低于10-2Pa，将Si基底置于反应腔中，调节温度至980℃，将氨气和三甲基镓加热后以气体的形式通入反应器中，氨气和三甲基镓的体积比为130:1，在基底上制备厚度5μm的GaN外延层；
3、调节温度至1000℃，控制NH3:三甲基镓进气量比为130:1，通入气体锗烷，锗烷气量为总气量的0.3%，在GaN外延层上制备厚度1μm的p型半导体材料层；
4、准备与步骤3中材料大小相同，厚度为3μm的带条形孔、孔间距2mm的钛片，并覆盖于步骤3的p型半导体材料层表面，在950℃下，控制NH3: 三甲基镓进气量比为130:1，通入气体锗烷，锗烷为总气量的0.3%，在p型半导体材料层上制得间距2mm、厚度3μm的条块状n型半导体材料层，去掉钛片后置于去离子水中保存；
5、配制含有0.1mol/L的硫酸铅、0.01mol/L的硫酸铜、0.01mol/L硼酸的电解液，将步骤4制得的材料置于电解液中作为工作极，铂电极和饱和甘汞电极分别作为对电极与参比电极，在-0.3V电位下沉积30min，在n型半导体材料表层及n型半导体材料间隙中的p型半导体材料表层形成厚度2μm铅铜合金层催化层，制得阳电极；
采用三电极体系，制备的阳电极为工作电极（导线接p型材料层），银丝为参比电极，铂网作为对电极，以0.2mol/L NaOH及0.1mol/L氨水配置成吸收液并作为电解质，通入被测气体后开始测量，采用线性伏安法设定采样间隔0.1s，扫描范围-0.3-1V，NO2与SO2对应的峰位置为0.7V与0.2V，其峰高度（电流大小）与通入气体浓度成正比，结果见图3、4。
Claims (8)
1.一种自发光的光电协同催化电极，其特征在于：包括基底、外延层、n型半导体材料层、p型半导体材料层、催化材料层，当电极为阳电极时，基底上覆盖一层厚度3~5μm外延层，厚度1~3μm 的p型半导体材料层设置在外延层上，厚度1~3μm的n型半导体材料层设置在p型半导体材料层上，n型半导体材料层是由若干条间距相等的条块组成，催化材料层设置在n型半导体材料层和p型半导体材料层上，厚度为1~2μm；
当电极为阴电极时，基底上覆盖一层厚度3~5μm的外延层，厚度1~3μm的n型半导体材料层设置在外延层上，厚度为1~3μm p型半导体材料层设置在n型半导体材料层上，p型半导体材料层是由若干条间距相等的条块组成，催化材料层设置在p型半导体材料层和n型半导体材料层上，厚度为1~2μm。
2.根据权利要求1所述的自发光的光电协同催化电极，其特征在于：基底为Al2O3、SiC、聚二甲基硅氧烷、Si中的一种；外延层的材料是选择n型半导体材料层或p型半导体材料层中原子序数最高的两种元素制备而成。
3.根据权利要求1所述的自发光的光电协同催化电极，其特征在于：n型半导体材料层的材料是在Ⅲ族元素和Ⅴ族元素中掺入O、S、Se、Te、C、Si、Ge中一种或几种制得，O、S、Se、Te、C、Si、Ge的掺入量为n型半导体材料总摩尔量的10-9-1%；
或是在Ⅱ族元素和Ⅵ族元素中掺入Cl、Br、I中一种或几种制得，Cl、Br、I的掺入量为n型半导体材料总摩尔量的10-9-1%；
或是在Ⅱ族元素和Ⅵ族元素中掺入B、Al、Ga、In中一种或几种制得， B、Al、Ga、In中一种或几种的掺入量为n型半导体材料总摩尔量的10-9-1%。
4.根据权利要求1所述的自发光的光电协同催化电极，其特征在于：p型半导体材料层的材料在Ⅲ族元素和Ⅴ族元素中掺入Zn、Be、Mg、Cd中一种或几种制得，Zn、Be、Mg、Cd中一种或几种的掺入量为p型半导体材料总摩尔量的10-9-1%；
或是在Ⅱ族元素和Ⅵ族元素中掺入Li、Na、K中一种或几种制得，Li、Na、K中一种或几种的掺入量为p型半导体材料总摩尔量的10-9-1%；
或是在Ⅱ族元素和Ⅵ族元素中掺入N、P、As、Sb、Bi中一种或几种制得，N、P、As、Sb、Bi中一种或几种的掺入量为p型半导体材料总摩尔量的10-9-1%。
5.根据权利要求2或3所述的自发光的光电协同催化电极，其特征在于：Ⅲ族元素为B、Al、Ga、In中的一种或几种，Ⅴ族元素为N、P、As、Sb、Bi中的一种或几种，Ⅱ族元素为Zn、Mg、Cd、Be中的一种或几种，Ⅵ族元素为O、S、Se、Te中的一种或几种。
6.根据权利要求1所述的自发光的光电协同催化电极，其特征在于：n型半导体材料或p型半导体材料中所有元素加权平均原子序Z≤40。
7.根据权利要求1所述的自发光的光电协同催化电极，其特征在于：催化材料层由d区元素、d区元素的氧化物中的一种或几种组成；或先由d区元素、d区元素的氧化物中的一种或几种形成底层，再在底层上形成表层，且底层元素的序数比表层元素序数高。
8.权利要求1-7中任一项所述的自发光的光电协同催化电极在废水处理、电化学合成、电化学检测中的应用。
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| CN117263364A (zh) * | 2023-10-20 | 2023-12-22 | 昆明理工大学 | 一种外场协同微生物降解污水中有机磷、有机氯及苯系有机污染物装置及装置制备方法 |
| CN117263364B (zh) * | 2023-10-20 | 2024-03-22 | 昆明理工大学 | 一种外场协同微生物降解污水中有机磷、有机氯及苯系有机污染物装置及装置制备方法 |
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