CN113648999A - 一种金属气凝胶材料的制备方法及其应用 - Google Patents
一种金属气凝胶材料的制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 24
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 21
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
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- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
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- 238000003756 stirring Methods 0.000 claims abstract description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 230000001699 photocatalysis Effects 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
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- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
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- 239000010931 gold Substances 0.000 description 7
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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Abstract
本发明公开一种金属气凝胶材料的制备方法及其应用。首先将金属盐加入去离子水中搅拌分散，再加入乙醇进行稀释，得到金属盐溶液；然后将溶于乙醇中的硼氢化钠溶液快速注入金属盐溶液中，颜色立刻变成黑色；25～35分钟后，黑色凝胶沉在反应器底部，分离黑色凝胶，洗涤后进行冷冻干燥，得到固体气凝胶，即金属气凝胶材料。与目前的合成方法相比，本发明方法不必使用有害的有机溶剂和昂贵的添加剂，具有更优的经济效益和环保性。与此同时，本发明方法可以在短时间内生产更多的金属气凝胶，凝胶时间的缩短和反应体积的降低，便于多批进行，显著提高了生产效率。
Description
技术领域
本发明涉及金属光催化材料，特别涉及一种金属气凝胶材料的制备方法及其应用。
背景技术
随着科技的不断进步，能源问题对人们带来的威胁日益增加。在不使用化石资源的前提下转化和储存能量需要创新的技术，太阳能驱动的光催化二氧化碳还原反应不仅产生了高附加值的化学物质，而且还减少了二氧化碳的排放。由于二氧化碳分子的高化学惰性和光诱导载流子的快速重组，光转化反应需要一系列通用的高性能材料。
气凝胶材料是一种具有超低密度、大比表面积、大量互联开放孔隙的超多孔材料。这些新型的纳米结构不仅结合了纳米材料的物理化学特性，而且在不同的尺寸、组成和形态效应方面具有优异的特性。与将金属负载在传统的无金属气凝胶如金属氧化物，碳材料等相比，无支撑的纯金属气凝胶的设计和合成非常有限，这对材料工程具有重要的意义。与基于碳负载的材料相比，金属的特性和结构保证了更高的耐腐蚀性和更长的耐久性，同时对催化反应的活性和选择性有益，纯金属的气凝胶是一种具有很大应用前景的材料。
但是金属气凝胶目前的生产方法大多比较复杂和繁琐，还需要用到有害的有机溶剂和昂贵的添加剂。
发明内容
针对目前金属气凝胶复杂，高成本的合成方法及传统气凝胶负载金属光催化活性的缺陷，本发明提供一种金属气凝胶材料的制备方法及其在光催化还原二氧化碳中的应用，以乙醇取代有害有机溶剂，且不使用昂贵添加剂，所制备的纯金属气凝胶的光催化二氧化碳活性明显提升。本发明方法成本低廉，操作方便，工艺简单，绿色环保。
本发明的技术方案为:
一种金属气凝胶材料的制备方法，包括如下步骤：
(1)将金属盐加入去离子水中搅拌分散，再加入乙醇进行稀释，得到金属盐溶液；
(2)将硼氢化钠溶解在乙醇中，得到硼氢化钠溶液；
(3)将步骤(2)所得硼氢化钠溶液快速注入步骤(1)所得金属盐溶液中，颜色立刻变成黑色；
(4)25～35分钟后，黑色凝胶沉在反应器底部，分离黑色凝胶，洗涤后进行冷冻干燥，得到固体气凝胶，即金属气凝胶材料。
进一步地，金属盐与硼氢化钠的物质的量之比为0.4～0.6:1.5～2.5。
进一步地，步骤(1)中，所述金属盐为氯化铜、氯化钴、氯化钯、氯化铂、氯化金或硝酸银中的一种或两种以上。
进一步地，步骤(4)中，所述洗涤具体为：用水和乙醇分别洗涤2～5次去除黑色凝胶中剩余的残留物。
进一步地，步骤(4)中，所述冷冻干燥具体为：在-80～-60℃冷冻干燥10～16小时。
上述制备方法得到的金属气凝胶材料应用于光催化还原二氧化碳中。
本发明的有益效果在于：
(1)传统的金属气凝胶合成方法中，要么额外加入了稳定剂，要么没有使用任何的封端剂。将乙醇作为反应溶剂时，乙醇对离子和金属纳米粒子的介电常数发生改变，因此导致封端和电荷稳定行为发生变化。鉴于这一特性，在本发明中，我们采用乙醇作为溶剂，简便的，不加稳定剂的一步合成了多种纯的金属气凝胶。
(2)本发明方法制备的纯金属气凝胶光催化材料相较于传统的金属材料，得益于其超多孔隙的结构和较大的比表面积，其光催化还原二氧化碳的性能有着极大的提升。
与目前的合成方法相比，本发明方法不必使用有害的有机溶剂和昂贵的添加剂，具有更优的经济效益和环保性。与此同时，本发明方法可以在短时间内生产更多的金属气凝胶，凝胶时间的缩短和反应体积的降低，便于多批进行，显著提高了生产效率。
附图说明
图1为Pt、Pd、Au的XRD衍射图，均显示出单一的金属相，表明纯的金属气凝胶的制备。
图2为Ag、Cu、Co的XRD衍射图，由于空气的氧化Cu显示出Cu2O的晶相，由于非晶形的结构，Co没显示出任何的衍射峰。
图3为Pt、Pd、Au、Ag、Cu、Co的SEM图，从扫描电镜图像中可以看到金属凝胶的多孔特性，所有气凝胶均表现出具有海绵状形态的三维网络结构。Pt、Pd和Co形成了更粗糙的表面，而Au和Ag显示出光滑的表面，这取决于金属的晶体结构。
图4为金属光催化还原二氧化碳的活性表征图，所制备的纯金属气凝胶均表现出了优异的光催化活性，最高的一氧化碳产率可达2232.15μmol g-1h-1。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但本发明并不限于此。
实施例1
首先将0.5mmol的氯化铜加入到10mL的去离子水中搅拌分散，配制成50mmol/L的氯化铜溶液。在用30mL的乙醇稀释该溶液。其次，将2mmol的硼氢化钠溶解在40mL的乙醇中。随后，将制备的硼氢化钠溶液快速的注入到氯化铜溶液中，颜色立刻变成黑色。30分钟后，一个黑色的凝胶沉在烧杯的底部，将产物用水和乙醇分别洗涤三次去除剩余的残留物，并在-70℃冷冻干燥12小时以获得铜金属气凝胶材料。
实施例2
首先将0.4mmol的硝酸银加入到10mL的去离子水中搅拌分散，并用30mL的乙醇稀释该溶液。其次，将1.6mmol的硼氢化钠溶解在32mL的乙醇中。随后，将制备的硼氢化钠溶液快速的注入到硝酸银溶液中，颜色立刻变成黑色。30分钟后，一个黑色的凝胶沉在烧杯的底部，将产物用水和乙醇分别洗涤三次去除剩余的残留物，并在-60℃冷冻干燥13小时以获得银金属气凝胶材料。
实施例3
首先将0.6mmol的氯化钴加入到10mL的去离子水中搅拌分散，并用30mL的乙醇稀释该溶液。其次，将2.4mmol的硼氢化钠溶解在48mL的乙醇中。随后，将制备的硼氢化钠溶液快速的注入到氯化钴溶液中，颜色立刻变成黑色。25分钟后，一个黑色的凝胶沉在烧杯的底部，将产物用水和乙醇分别洗涤三次去除剩余的残留物，并在-50℃冷冻干燥15小时以获得钴金属气凝胶材料。
实施例4
首先将0.5mmol的氯化金加入到10mL的去离子水中搅拌分散，并用30mL的乙醇稀释该溶液。其次，将2mmol的硼氢化钠溶解在30mL的乙醇中。随后，将制备的硼氢化钠溶液快速的注入到氯化金溶液中，颜色立刻变成黑色。30分钟后，一个黑色的凝胶沉在烧杯的底部，将产物用水和乙醇分别洗涤三次去除剩余的残留物，并在-80℃冷冻干燥10小时以获得金金属气凝胶材料。
实施例5
首先将0.6mmol的氯化铂加入到10mL的去离子水中搅拌分散，并用30mL的乙醇稀释该溶液。其次，将2.4mmol的硼氢化钠溶解在48mL的乙醇中。随后，将制备的硼氢化钠溶液快速的注入到氯化铂溶液中，颜色立刻变成黑色。25分钟后，一个黑色的凝胶沉在烧杯的底部，将产物用水和乙醇分别洗涤三次去除剩余的残留物，并在-70℃冷冻干燥12小时以获得铂金属气凝胶材料。
实施例6
首先将0.4mmol的氯化钯加入到10mL的去离子水中搅拌分散，并用30mL的乙醇稀释该溶液。其次，将1.6mmol的硼氢化钠溶解在24mL的乙醇中。随后，将制备的硼氢化钠溶液快速的注入到氯化钯溶液中，颜色立刻变成黑色。30分钟后，一个黑色的凝胶沉在烧杯的底部，将产物用水和乙醇分别洗涤三次去除剩余的残留物，并在-60℃冷冻干燥12小时以获得钯金属气凝胶材料。
图1为Pt、Pd、Au的XRD衍射图，均显示出单一的金属相，表明纯的金属气凝胶的制备。
图2为Ag、Cu、Co的XRD衍射图，由于空气的氧化Cu显示出Cu2O的晶相，由于非晶形的结构，Co没显示出任何的衍射峰。
图3为Pt、Pd、Au、Ag、Cu、Co的SEM图，从扫描电镜图像中可以看到金属凝胶的多孔特性，所有气凝胶均表现出具有海绵状形态的三维网络结构。Pt、Pd和Co形成了更粗糙的表面，而Au和Ag显示出光滑的表面，这取决于金属的晶体结构。
图4为金属光催化还原二氧化碳的活性表征，所制备的纯金属气凝胶均表现出了优异的光催化活性，最高的一氧化碳产率可达2232.15μmol g-1h-1。
致谢
本发明是在湖南省科技创新计划项目(项目编号为2020RC2076)的资助下完成的，特此感谢湖南省科技厅对本发明的帮助。
Claims (6)
1.一种金属气凝胶材料的制备方法，其特征在于，包括如下步骤：
(1)将金属盐加入去离子水中搅拌分散，再加入乙醇进行稀释，得到金属盐溶液；
(2)将硼氢化钠溶解在乙醇中，得到硼氢化钠溶液；
(3)将步骤(2)所得硼氢化钠溶液快速注入步骤(1)所得金属盐溶液中，颜色立刻变成黑色；
(4)25～35分钟后，黑色凝胶沉在反应器底部，分离黑色凝胶，洗涤后进行冷冻干燥，得到固体气凝胶，即金属气凝胶材料。
2.根据权利要求1所述的金属气凝胶材料的制备方法，其特征在于，金属盐与硼氢化钠的物质的量之比为0.4～0.6:1.5～2.5。
3.根据权利要求1所述的金属气凝胶材料的制备方法，其特征在于，步骤(1)中，所述金属盐为氯化铜、氯化钴、氯化钯、氯化铂、氯化金或硝酸银中的一种或两种以上。
4.根据权利要求1所述的金属气凝胶材料的制备方法，其特征在于，步骤(4)中，所述洗涤具体为：用水和乙醇分别洗涤2～5次去除黑色凝胶中剩余的残留物。
5.根据权利要求1所述的金属气凝胶材料的制备方法，其特征在于，步骤(4)中，所述冷冻干燥具体为：在-80～-60℃冷冻干燥10～16小时。
6.权利要求1至5任一项所述的制备方法得到的金属气凝胶材料在光催化还原二氧化碳中的应用。
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