CN112844479A - 一种zif-8负载银纳米颗粒催化剂及其制备方法和应用 - Google Patents
一种zif-8负载银纳米颗粒催化剂及其制备方法和应用 Download PDFInfo
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 85
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- AAORDHMTTHGXCV-UHFFFAOYSA-N uranium(6+) Chemical compound [U+6] AAORDHMTTHGXCV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及光催化剂还原铀技术领域，具体涉及一种ZIF‑8负载银纳米颗粒催化剂及其制备方法和应用。所述催化剂的制备方法包括以下步骤：S1:将硝酸锌与2‑甲基咪唑溶于甲醇中超声并搅拌混合均匀，静置18‑28h，过滤取沉淀物，经洗涤、干燥获得ZIF‑8；S2:将所述ZIF‑8与硝酸银加入至甲醇和乙醇的混合溶剂中，经溶剂热还原反应，过滤取沉淀物，经洗涤、干燥获得ZIF‑8负载银纳米颗粒催化剂。本发明制备获得的ZIF‑8负载银纳米颗粒催化剂在无任何牺牲剂的条件下用于光催化还原铀时，催化剂性质稳定、催化活性高，能多次重复利用。
Description
技术领域
本发明涉及光催化剂还原铀技术领域，具体涉及一种ZIF-8负载银纳米颗粒催化剂及其制备方法和应用。
背景技术
随着核工业的快速发展，放射性污染已成为最复杂的环境问题之一。铀是典型的放射性污染物，从铀矿开采、核研究、燃料生产和武器制造释放。长期接触铀会导致严重的健康问题，如严重的肝脏损伤、肾脏损伤，并最终导致死亡。因此，环境中暴露铀的清除是一个重要的问题。研究表明，铀矿物可以以多种氧化态存在(如U(0)、U(III)、U(IV)和U(VI))，其中环境中的主要氧化态为可溶性U(VI)和轻度可溶性U(IV)。将可溶性铀(VI)还原为不溶性铀(IV)氧化物是消除放射性污染的重要途径。
经研究，多相光催化降解废水中有害污染物已被证明是一种有效的方法，等离子体催化是多相光催化的一个重要分支，它通过等离子体金属纳米粒子(如Ag、Au、Cu)的局域表面等离子体共振(LSPR)效应有效地加速光化学反应的发生，等离子体催化剂对氮光固定、二氧化碳光还原和光催化水分解等一系列光化学反应表现出显著的催化性能，在光还原U(VI)过程中，等离子体催化应用的主要障碍是等离子体金属纳米颗粒上糟糕的吸附位点和较差的载体分离效率，现有技术中将等离子体金属纳米粒子与半导体的集成以提高载体分离效率；特别是对U(VI)具有较强吸附能力的半导体，有利于进一步提高铀的富集动力学和富集能力。此外，材料的稳定性和可重复使用性也是评价其能否在实际工程中应用的重要指标。
因此，构建新型等离子体金属半导体复合材料以实现良好的铀还原效率和稳定性是迫切需要的，但仍是一个巨大的挑战。
发明内容
针对现有技术存在的上述问题，本发明将银纳米颗粒负载在ZIF-8上获得ZIF-8负载银纳米颗粒催化剂，其用于光催化还原铀时，催化剂性质稳定、催化活性高，能多次重复利用。
为实现上述发明目的，本发明提供了一种ZIF-8负载银纳米颗粒催化剂的制备方法，具体包括以下步骤：
S1:将硝酸锌与2-甲基咪唑溶于甲醇中超声并搅拌混合均匀，静置18-28h，过滤取沉淀物，经洗涤、干燥获得ZIF-8；
S2:将所述ZIF-8与硝酸银加入至甲醇和乙醇的混合溶剂中，经溶剂热还原反应，过滤取沉淀物，经洗涤、干燥获得ZIF-8负载银纳米颗粒催化剂。
进一步的，所述步骤S2中甲醇和乙醇的体积比为1:0.8-1.2。
进一步的，所述步骤S2中溶剂热还原反应的工艺参数为：温度为150-160℃，时间为3-5h。
进一步的，所述步骤S1和步骤S2中干燥为真空干燥，工艺参数为：温度为50-65℃，时间为6-10h。
基于同一发明思路的，本发明还提供了一种ZIF-8负载银纳米颗粒催化剂，所述催化剂由上述制备方法制备获得。
进一步的，所述银纳米颗粒的负载量为4-6wt％。
本发明还提供了上述ZIF-8负载银纳米颗粒催化剂的应用，将其用于光催化还原铀。
有益效果：
(1)本发明以Ag作为金属元素，以ZIF-8为载体，其中Ag具有LSPR效应，成为等离子体催化剂中极具吸引力的电子供体，ZIF-8作为提提，具丰富的含单集团作为大量还原的位点，与纳米颗粒Ag结合可以促进热电子分离并有效转移到吸附U(VI)上，解决了LSPR效应产生的热电子存在衰退速度快的问题，催化剂在受到光照后，在不使用牺牲剂的情况下实现U(VI)的还原。
(2)本发明提供的ZIF-8负载银纳米颗粒催化剂的制备方法简单，负载率高，原料常规易得，具有环保性。
(3)本发明提供的ZIF-8负载银纳米颗粒催化剂为一种具有高活性、稳定性的油富集光催化剂，在自然阳光照射下，该催化剂能富集85.8％以上的U(VI)，在环境保护的实际应用中具有显著的潜力。
附图说明
图1为本发明实施例提供的Ag/ZIF-8的微观结构图；
图2为本发明实施例提供的Ag/ZIF-8和ZIF-8的铀吸附率和去除率的时间曲线图；
图3为本发明实施例提供的Ag/ZIF-8的循环使用稳定性图；
图4为本发明实施例提供的Ag/ZIF-8在不同初始铀浓度下的去除率和容量图；
图5为本发明实施例提供的Ag/ZIF-8在10ppm铀浓度下10倍共存离子的去除率图；
图6为本发明实施例提供的Ag/ZIF-8在10ppm铀浓度下不同pH值的去除率图；
图7为本发明实施例提供的Ag/ZIF-8在自然日光实验下的去除率图；
图8为本发明实施例提供的Ag/ZIF-8和ZIF-8的uv图；
图9为本发明实施例提供的Ag/ZIF-8黑暗吸附与打光反应后的XPS图谱；
图10为本发明实施例提供的Ag/ZIF-8反应机理示意图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合具体实施例进行详细描述，但本发明的保护范围并不限于以下具体实施例。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
本发明中ZIF-8的结构式如式Ⅰ所示。
实施例1
S1:ZIF-8制备：
(1)称量3.7g六水硝酸锌、4.1g 2-甲基咪唑；
(2)将称量好的粉末溶于500ml甲醇中，超声并搅拌使其混合均匀；
(3)将溶液静置24h，得到白色沉淀物；
(4)冷却后，用大量去离子水抽滤洗涤，60℃真空干燥8h，得到ZIF-8。
S2:ZIF-8负载银纳米颗粒催化剂Ag/ZIF-8制备：
(1)称量7.9mg硝酸银、95mg ZIF-8；
(2)将称量好的粉末溶于35ml甲醇中，然后再加入35ml乙醇，超声并搅拌一夜使其混合均匀；
(3)将溶液倒入反应釜中，160℃保温5h；
(4)冷却后，用去离子水抽滤洗涤，60℃真空干燥8h，得到Ag/ZIF-8催化剂。
对比例1
(1)称量3.7g六水硝酸锌、4.1g 2-甲基咪唑；
(2)将称量好的粉末溶于500ml甲醇中，超声并搅拌使其混合均匀；
(3)将溶液静置24h，得到白色沉淀物；
(4)冷却后，用大量去离子水抽滤洗涤，60℃真空干燥8h，得到ZIF-8。
应用例：
将实施例1获得的Ag/ZIF-8催化剂和对比例1获得的ZIF-8催化剂应用至光催化还原铀。具体步骤如下：
(1)取5mg制备的Ag/ZIF-8或ZIF-8催化剂加入到20mL铀溶液中(U6+200ppm)；
(2)随后在光照强度为250mW·cm-2的氙灯下边照射边剧烈搅拌60min，在规定的时间内取样，离心后用偶氮胂Ⅲ显色法检测剩余溶液的六价铀浓度。
经检测，Ag/ZIF-8对初始浓度200ppm铀溶液的铀去除率高达92.8％，ZIF-8对初始浓度200ppm铀溶液的铀富集率为57.6％。
采用扫描电镜观测Ag/ZIF-8微观结构，如图1所示，可以得出ZIF-8呈现出多面体结构，Ag以纳米颗粒的形式均匀负载在ZIF-8上。
将5mgAg/ZIF-8、5mg ZIF-8加入至铀溶液中(U6+200ppm)，分别在无光照和氙灯照射条件下处理60min后，测定剩余溶液的六价铀浓度，其结果如图2所示，在无光照条件下，Ag/ZIF-8的吸附量与ZIF-8相似，60min后萃取质量为433.6mg/g。当玻璃反应器用氙灯照射时，ZIF-8显示出与没有光照时几乎相同的富集能力。相比之下，Ag/ZIF-8对U(VI)的富集能力在光照下显著提高，在初始浓度为200ppm的U(VI)溶液中，去除率为92.8％。
将上述Ag/ZIF-8U(VI)光还原实验结束后采集样品，在100mL 0.1mol/L Na2CO3溶液中超声处理2h，干燥进入下一个循环，其结果如图3所示，由此可知Ag/ZIF-8连续5轮后初始去除率大于85.6％，具有良好的稳定性和可重复使用性。
对于不同初始浓度的铀溶液，用Ag/ZIF-8进行光催化实验，其结果如图4所示，可知Ag/ZIF-8在初始浓度为0.5ppm～400ppm的U(VI)溶液中表现出显著的去除率。U(VI)浓度在60min内从1ppm和0.5ppm下降到23.3ppb和17.4ppb，低于世界卫生组织(WHO)规定的饮用水标准(30ppb)。更重要的是，当U(VI)初始浓度为400ppm时，Ag/ZIF-8无饱和萃取质量可达1532.8mg/g。
配置含有10倍量的不同价态的碱土金属、过度金属、稀土元素的含铀溶液(U6+10ppm)，采用Ag/ZIF-8进行光照催化实验，其结果如图5所示。其结果表明在上述溶液中铀仍能有效的分离，说明本发明的Ag/ZIF-8催化剂具有良好的选择性。
配置不同pH值的含铀溶液(U6+10ppm)，采用Ag/ZIF-8进行光催化实验，其结果如图6所示。其结果表明，Ag/ZIF-8在酸性、中性下都能表现出显著的去除率。
将Ag/ZIF-8加入至含铀溶液(U6+10ppm)中，并在自然光照射下进行光催化实验，其结果如图7所示。由此可知，Ag/ZIF-8在一天内富集了85.8％以上的U(VI)，在环境保护的实际应用中具有显著的潜力。做到以太阳光而不是氙灯作为能量输入，减少了能源消耗、增强了可操作性。
将Ag/ZIF-8和ZIF-8在不同波长的光的照射下进行铀溶液的光催化实验，其结果如图8所示。由此可知，ZIF-8只吸收波长小于250nm的光。Ag/ZIF-8由于Ag纳米颗粒的LSPR效应，在200～500nm范围内可以观察到较强的光吸收。
将测定Ag/ZIF-8在黑暗吸附与打光反应后的XPS图谱，其结果如图9所示，结果表明，只有在打光条件下，六价铀才可以被还原为四价铀。如图10所示，其为Ag/ZIF-8催化还原铀的反应机理示意图，在光照条件下，ZIF-8中的含氮基团是高效吸附U(VI)物种的活性位点，通过LSPR效应在Ag纳米颗粒上产生的热电子转化为ZIF-8，使得Ag/ZIF-8的优异性能。
以上所述实施例，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明的技术范围内，根据本发明的技术方案及其构思加以等同替换或改变，都应涵盖在本发明的保护范围内。
Claims (7)
1.一种ZIF-8负载银纳米颗粒催化剂的制备方法，其特征在于，具体包括以下步骤：
S1:将硝酸锌与2-甲基咪唑溶于甲醇中超声并搅拌混合均匀，静置18-28h，过滤取沉淀物，经洗涤、干燥获得ZIF-8；
S2:将所述ZIF-8与硝酸银加入至甲醇和乙醇的混合溶剂中，经溶剂热还原反应，过滤取沉淀物，经洗涤、干燥获得ZIF-8负载银纳米颗粒催化剂。
2.根据权利要求1所述的ZIF-8负载银纳米颗粒催化剂的制备方法，其特征在于，所述步骤S2中甲醇和乙醇的体积比为1:0.8-1.2。
3.根据权利要求1所述的ZIF-8负载银纳米颗粒催化剂的制备方法，其特征在于，所述步骤S2中溶剂热还原反应的工艺参数为：
温度为150-160℃，时间为3-5h。
4.根据权利要求1所述的ZIF-8负载银纳米颗粒催化剂的制备方法，其特征在于，所述步骤S1和步骤S2中干燥为真空干燥，工艺参数为：
温度为50-65℃，时间为6-10h。
5.一种ZIF-8负载银纳米颗粒催化剂，其特征在于，所述催化剂由权利要求1-4任一所述制备方法制备获得。
6.根据权利要求5所述的ZIF-8负载银纳米颗粒催化剂，其特征在于，所述银纳米颗粒的负载量为4-6wt％。
7.权利要求1-4任一所述制备方法获得的ZIF-8负载银纳米颗粒催化剂和权利要求5-6任一所述的ZIF-8负载银纳米颗粒催化剂的应用，其特征在于，所述催化剂用于光催化还原铀。
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