CN114772630A - 一种微纳米结构的氧化镓、其制备方法及应用 - Google Patents
一种微纳米结构的氧化镓、其制备方法及应用 Download PDFInfo
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Abstract
本案涉及一种微纳米结构的氧化镓、其制备方法及应用，在反应瓶中加入DL‑天冬氨酸和去离子水，超声溶解，然后向该溶液中依次加入PEG溶液、硝酸镓溶液和尿素，搅拌混合均匀后得无色澄清透明溶液；加热至沸腾，调节溶液的pH值为6，体系呈溶胶状；水洗干燥得前驱体材料；煅烧得α‑Ga2O3纳米材料。本发明以PEG‑4000和DL‑天冬氨酸为复合软模板剂，合成出了形貌、尺寸较为均一的GaOOH纳米晶体微球体结构，粒径为500nm。微球状的GaOOH纳米结构经煅烧后，可以获得形貌保持良好的α‑Ga2O3微球体，其对甲基紫水溶液的脱色率为99.85％，说明实验制备的α‑Ga2O3微球体具有良好的光催化性能。
Description
技术领域
本发明涉及纳米金属氧化物的制备技术领域，具体涉及一种微纳米结构的氧化镓、其制备方法及应用。
背景技术
纳米金属半导体氧化物在传感检测、污水处理、空气净化等领域有广泛应用，其制备方法的选择、形貌和尺寸的控制仍是当今纳米科技和环境化学领域的研究热点。纳米氧化镓(Ga2O3)是一种N型宽带隙(4.7-4.9eV)的半导体氧化物，在光电子器件、传感器以及催化领域都有广泛的应用前景，而纳米氧化镓用于废水处理的研究相对较少，如何控制氧化镓纳米材料的形貌、尺寸进而影响纳米氧化镓的光催化性能，科研工作者们一直在探索。目前，已报道的纳米氧化镓的制备方法有共沉淀法、热蒸发法、化学气相沉积(CVD)法、热退火法、水热合成法、微波法等。低温水热法是液相法中制备纳米粒子最简单有效的方法之一，目前已报道的水热合成纳米氧化镓的方法中，Ga2O3形貌和尺寸的控制主要是通过温度、pH值或通过有机溶剂和表面活性剂来调控的。
发明内容
针对现有技术中的不足之处，本发明提供了一种微纳米结构的氧化镓、其制备方法及应用。
为实现上述目的，本发明提供如下技术方案：
一种微纳米结构的氧化镓的制备方法，包括如下步骤：
S1：向反应瓶中加入DL-天冬氨酸和去离子水，超声溶解，然后向该溶液中依次加入PEG溶液、硝酸镓溶液和尿素，搅拌混合均匀后得无色澄清透明溶液；DL-天冬氨酸和PEG的质量比为0.04:0.4-0.04:6；
S2：将无色澄清透明溶液然后从室温起加热至沸腾，直至体系中出现白色沉淀且浑浊度不再增加时调节溶液的pH值为6，体系呈溶胶状；
S3：将体系保持沸腾状态继续搅拌3h后停止加热，自然冷却至室温，经10h左右自然沉降后分离沉淀物并先后用蒸馏水和无水乙醇各洗涤3次，最后于60℃条件下真空干燥12h，得前驱体材料；
S4：将前驱体材料装入刚玉坩埚并置于马弗炉中，在450℃条件下煅烧3h后得α-Ga2O3纳米材料。
进一步地，所述PEG分子量为4000，配制成PEG溶液的浓度为0.1mol/L。
进一步地，硝酸镓溶液的浓度为0.2mol/L，与DL-天冬氨酸的体积质量比为0.5ml:0.02g～0.5ml:0.05g。
本发明进一步提供一种如上所述的制备方法制得的微纳米结构的氧化镓。
本发明进一步提供一种如上所述的微纳米结构的氧化镓的应用，该氧化镓可用于对染料废水的光催化降解。
本发明的有益效果是：本发明以PEG-4000和DL-天冬氨酸为复合软模板剂，通过简单的常压回流方式合成出了形貌、尺寸较为均一的GaOOH纳米晶体微球体结构，粒径为500nm。微球状的GaOOH纳米结构经煅烧后，可以获得形貌保持良好的α-Ga2O3微球体，其对甲基紫水溶液在100min内的脱色率为99.85％，说明实验制备的α-Ga2O3微球体具有良好的光催化性能。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1制得的前驱体材料和氧化镓材料的XRD谱图。
图2(b、c)分别为GaOOH纳米晶体和α-Ga2O3的FE-SEM照片图。
图3(a、b)分别为GaOOH纳米晶体和α-Ga2O3的FT-IR谱图和荧光发射光谱图。
图4为对比例1制得的前驱体材料的FE-SEM图(a、b)和TEM图(c、d)。
图5为对比例2制得的前驱体材料的FE-SEM图(a、b)和TEM图(c、d)。
图6为对比例3制得的前驱体材料的FE-SEM图(a、b)和TEM图(c、d)。
图7为α-Ga2O3微球体光催化降解甲基紫的紫外-可见光谱(a)及光催化降解甲基紫的吸光率-时间曲线(b)图。
具体实施方式
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
实施例1
S1：向50mL圆底烧瓶中加入0.0400g DL-天冬氨酸和4.50mL的去离子水，超声溶解，然后向该溶液中依次加入5.00mL(0.1mol/L)PEG-4000溶液、0.50mL(0.2mol/L)硝酸镓溶液和0.3003g的尿素，搅拌混合均匀后得无色澄清透明溶液；
S2：无色澄清透明溶液从室温起加热至沸腾，经15min后肉眼可见体系中开始有白色沉淀出现，体系的浑浊度随回流时间增长而加剧，浑浊度不再增加时溶液的pH值约为6，体系呈溶胶状；
S4：将体系保持沸腾状态继续搅拌3h后停止加热，自然冷却至室温，经10h左右自然沉降后分离沉淀物并先后用蒸馏水和无水乙醇各洗涤3次，最后于60℃条件下真空干燥12h，得前驱体材料；
S5：将前驱体材料装入刚玉坩埚并置于马弗炉中，在450℃条件下煅烧3h后得氧化镓粉末，留待后续表征和分析。
本发明以DL-天冬氨酸和PEG-4000为复合模板剂制备前驱体和氧化镓，如图1为前驱体及其煅烧后所得样品的XRD图谱。将前驱体的晶体粉末衍射图谱与GaOOH晶体的XRD标准图谱(JCPDS No.060180)进行比较，说明本实验方法所制备前驱体是GaOOH纳米晶体，图谱中35.72°(2θ)最强衍射峰对应GaOOH纳米晶体的(130)晶面，63.74°(2θ)较强衍射峰对应GaOOH晶体的(320)晶面。将前驱体GaOOH纳米晶体经450℃煅烧3h后所得的XRD图谱与PDF标准卡(JCPDS No.060503)吻合，说明前驱体煅烧后得到的样品是六方晶系α-Ga2O3晶体，其中XRD图谱上位于35.90°、63.33°的衍射峰分别对应α-Ga2O3的(110)晶面和(214)晶面。
图2b和图2c分别为GaOOH纳米晶体和α-Ga2O3的FE-SEM照片。从图中可明显观察到粒子呈微球状，其形貌和尺寸较为均一，组成紧致，表面光滑，直径分布范围为500nm左右，煅烧后的α-Ga2O3粒子具有良好的形貌及尺寸继承性。
图3a、b分别为GaOOH/α-Ga2O3微球体的FT-IR谱图和荧光发射光谱图。图3a可以看出在波数为3300～3400cm-1处的吸收带为H2O分子中H-O-H键的伸缩振动所致，1650cm-1附近有一个宽吸收带，可能为吸附的H2O分子中O-H键弯曲振动吸收带与样品中羟基振动吸收带的重叠，在2340cm-1左右处的微弱峰和1360cm-1左右处的吸收峰可以归属为样品吸附空气中CO2的C＝O对称结构，及954cm-1左右的吸收峰是由Ga-OH翻转变形产生的，643cm-1和510cm-1左右的吸收峰为α-Ga2O3中Ga-O结构的弯曲振动峰。
从图3b中可观察从320nm到约600nm的一个宽峰，其中有4个较明显的荧光发射峰，对应的波长分别为360nm左右的紫外光、406nm的紫光、472nm的蓝光以及510nm左右的绿光，且蓝光的峰强度相对较强。其中紫外发射源自自由电子与自陷空穴的复合，而α-Ga2O3的光致发光现象与结构中的Ga空位、O空位及Ga-O空位对(VO-VGa)有关。紫光和蓝光带可能源于α-Ga2O3中VO捕获的激发电子与VGa产生的受主能级空穴的复合，而绿光带则可能源自自陷激子或空位/缺陷束缚激子的弛豫现象。与商品α-Ga2O3晶体发射的蓝光500nm相比，我们制备的纳米α-Ga2O3发射的蓝光产生了明显的蓝移，该现象可能是由纳米材料的量子尺寸效应引起的，由于粒子尺寸降低，能隙宽度变大，从而导致发射光谱向短波长方向移动。
为了验证本案复合模板剂对材料的影响，本案提供如下对比实验。
对比例1：
与实施例1条件相同，区别在于只添加DL-天冬氨酸作为模板剂，经简单常压回流低温水热法制备得到前驱体材料。
如图4所示，与复合软模板诱导制备的GaOOH纳米晶体(实施例1)相比，形貌较不规则，球体尺寸较不均匀，疏松的微球体相互粘连，表面比较粗糙，且有少部分微球体尚未成型。图中微球体尺寸分布范围为150nm～300nm，与实施例1的微球体尺寸相比要小。从GaOOH微球体的TEM照片(图4c、d)可以看出，微球体组成较松散，粗糙的表面上纳米粒子的有序堆积，也侧面说明了微球体是由纳米小粒子自组装形成的。当体系中缺少PEG-4000作为控制粒子生长稳定剂时，Ga3+只是靠静电作用被DL-天冬氨酸分子分散于水介质中，从而在反应生成小粒子后易于发生小粒子生长或发生小粒子间的不规则聚集从而生成不规则的微球结构。
对比例2：
与实施例1条件相同，区别在于只添加PEG-4000作为模板剂，经简单常压回流低温水热法制备得到前驱体材料。
如图5所示，通过观察图中可看出，GaOOH晶体呈棒状、四棱柱结构，棒的长度和宽度分布范围分别为0.7μm～1.3μm，150nm～250nm，形貌和尺寸分布较为均一，表面比较粗糙，小粒子排列较不规整。与实施例1的GaOOH相比，该体系中因未加入有机小分子DL-天冬氨酸，不能利用其所含基团的静电引力作用将Ga3+拉到PEG-4000的表面，不能促进GaOOH纳米粒子在表面活性剂上进行有序堆积，同时也因缺少DL-天冬氨酸对生成GaOOH微粒的保护，难以得到聚集似球的实心颗粒，从而转为棒状形貌。
对比例3：
与实施例1条件相同，区别在于未添加任何模板剂，经简单常压回流低温水热法制备得到前驱体材料。
如图6所示，是反应体系经简单常压回流水热法制备的GaOOH的FE-SEM和TEM照片。从图4a、b可以看出，GaOOH晶体呈规则棒状，棒状结构较为疏松，棒的长度分布范围为0.7μm～1.1μm，形貌和尺寸较均一，于透射电镜照片图4c、d相吻合。
应用例：
称取0.0500g煅烧后的氧化镓粉末置于200mL石英反应瓶中，然后向其中加入50.00mL 10mg/L的甲基紫水溶液后转移至光反应仪内室，避光搅拌1h，使体系达到吸附-脱附平衡，然后25℃恒温水浴条件下，边搅拌边分别用波长为254nm、功率为150W的紫外灯和波长为420nm、功率为300W的氙灯进行光照(石英反应瓶距离光源均为10cm)，光照时间为100min，间隔20min取样，每次取5.0mL溶液，离心过滤后采用紫外-可见吸收光谱仪测定上层清液的吸收光谱。按下式将甲基紫溶液的吸光率转换成脱色率：
X＝(A0-At)/A0×100％
式中，A0—溶液的初始吸光率，At—t时刻溶液的吸光率。
从图7b曲线分析可知，在催化剂与甲基紫共同作用下，催化反应体系的吸光度随时间变化为线性下降。甲基紫的结构中含N-甲基，其易受OH·自由基的进攻发生脱甲基降解反应，表现在可见光区的最大吸收波长(λmax)蓝移。随光催化降解时间的延长，甲基紫可被矿化为NO2、CO2、H2O和其他无机离子，原因可能是：在紫外光照射下，价带上的电子被激发跃迁到导带，这样价带上就产生空穴，导带上形成光生电子。由于价带与导带之间存在禁带，空穴和光生电子在复合前有够长的寿命，迁移到光催化剂α-Ga2O3的表面。光生空穴具有很强的氧化性，可夺取吸附于α-Ga2O3颗粒表面上的水中电子使其生成HO·，而光生电子可迁移到α-Ga2O3微粒表面被氧化。上述反应可产生多种高反应活性的反应中间体和自由基，如HO·、·O2-、·O2 -和H2O2等，促使催化光照下的体系发生一系列有意义的氧化、还原反应，甲基紫分子被降解直到完全转化成CO2、NO2和H2O等小分子物质。
综上所述，本案以硝酸镓为镓源、尿素为均相沉淀剂，在PEG4000-DL-天冬氨酸复合软模板体系中，通过简单的常压回流方式成功合成出形貌、尺寸较为均一的GaOOH微球体结构，统计得粒径为500nm左右。实验显示，DL-天冬氨酸体系所制备的前驱体的形貌相对规则，粒径相对均匀且分布范围为150nm～300nm，近似微球体；PEG4000体系所制备的前驱体是截面为四棱柱型棒状结构，其形貌和尺寸分布比较均一，长度范围为0.7μm～1.3μm，宽度范围为150nm～250nm；无任何添加剂体系得到的GaOOH是长度分布范围为0.7μm～1.1μm的棒状结构微纳材料。结果表明，DL-天冬氨酸的添加及用量对GaOOH微球体形貌的保持和尺寸影响较大，而PEG4000的添加有利于形貌、尺寸均一微球的形成，说明在GaOOH和α-Ga2O3微球体纳米结构的控制合成中，由PEG4000-DL-天冬氨酸形成的复合软模板起着至关重要的作用，且在合适的配比条件下才能充分发挥其模板作用。微球状GaOOH纳米结构经煅烧后，可以获得形貌保持良好的α-Ga2O3微球体，其对甲基紫水溶液在100min内的脱色率为99.85％，说明实验制备的α-Ga2O3微球体具有良好的光催化性能。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节和这里示出与描述的图例。
Claims (5)
1.一种微纳米结构的氧化镓的制备方法，其特征在于，包括如下步骤：
S1：向反应瓶中加入DL-天冬氨酸和去离子水，超声溶解，然后向该溶液中依次加入PEG溶液、硝酸镓溶液和尿素，搅拌混合均匀后得无色澄清透明溶液；DL-天冬氨酸和PEG的质量比为0.04:0.4-0.04:6；
S2：将无色澄清透明溶液然后从室温起加热至沸腾，直至体系中出现白色沉淀且浑浊度不再增加时调节溶液的pH值为6，体系呈溶胶状；
S3：将体系保持沸腾状态继续搅拌3h后停止加热，自然冷却至室温，经10h左右自然沉降后分离沉淀物并先后用蒸馏水和无水乙醇各洗涤3次，最后于60℃条件下真空干燥12h，得前驱体材料；
S4：将前驱体材料装入刚玉坩埚并置于马弗炉中，在450℃条件下煅烧3h后得α-Ga2O3纳米材料。
2.如权利要求1所述的微纳米结构的氧化镓的制备方法，其特征在于，所述PEG分子量为4000，配制成PEG溶液的浓度为0.1mol/L。
3.如权利要求1所述的微纳米结构的氧化镓的制备方法，其特征在于，硝酸镓溶液的浓度为0.2mol/L，与DL-天冬氨酸的体积质量比为0.5ml:0.02g～0.5ml:0.05g。
4.一种如权利要求1-3中任一项所述的制备方法制得的微纳米结构的氧化镓。
5.如权利要求4所述的微纳米结构的氧化镓的应用，其特征在于，用于对染料废水的光催化降解。
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