CN114538501A - 氧空位缺陷的SnO2纳米材料的制备方法、氧空位缺陷的SnO2纳米材料及使用方法 - Google Patents
氧空位缺陷的SnO2纳米材料的制备方法、氧空位缺陷的SnO2纳米材料及使用方法 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 85
- 239000001301 oxygen Substances 0.000 title claims abstract description 85
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000007547 defect Effects 0.000 claims abstract description 22
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 18
- 229940012189 methyl orange Drugs 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000002950 deficient Effects 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 32
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 28
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000005067 remediation Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001432 tin ion Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910006733 SnO2Sn Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明公开了一种氧空位缺陷的SnO2纳米材料，及其制备、使用方法，本发明采用Sn2+为锡源，通过低温下的水热过程将其部分氧化为Sn4+，在SnO2晶格中引入氧空位缺陷。本发明获得的氧空位缺陷的SnO2在应用于吸附和光催化时展现出良好的性能，因氧空位的存在使其具有更宽的光响应范围、更强的光生电子和空穴分离效率、更多的表面吸附和氧化还原反应活性位点，可在环境修复方面发挥作用，对甲基橙的吸附效率为43.4％，模拟太阳光照6min对甲基橙的降解效率高达98.0％，对Cr(VI)的吸附效率为78.0％，模拟太阳光照4min对Cr(VI)的还原效率高达98.3％。本发明的氧空位缺陷的SnO2纳米材料是一种集优异的吸附和光催化活性于一体的光催化剂，其具有优异的吸附和光催化性能，能够应用于多个场景。
Description
技术领域
本发明涉及光催化纳米材料领域，尤其涉及氧空位缺陷的SnO2纳米材料的制备方法、氧空位缺陷的SnO2纳米材料及使用方法。
背景技术
从环境治理的角度来看，已存在许多方法应用于去除污染物，包括沉淀法、渗透法、吸附法、光催化法等。值得一提的是，其中吸附和光催化是两种重要的方式，但单纯的吸附仅仅将污染物从水中分离，并没有彻底的减少其潜在的危害。而光催化反应局限于光催化剂表面的传质过程，所以继续深入探索高效且连续的光催化系统有其价值所在。SnO2因其低成本、无毒、良好的化学稳定性、以及优异的导电性和光电性能等优势而备受关注。但SnO2作为n型宽带隙半导体(3.6eV)，仅能吸收紫外光，且光生电子和空穴分离效率低，在具体应用方面仍有待改进。SnO2晶格中的氧空位凭借其对材料微观电子结构的调整特性而在材料宏观光催化性能的提升方面做出了重要贡献。更重要的是，在催化剂表面存在的氧空位对光催化中污染物的吸附和降解均具有不可忽视的影响。因此，在SnO2中设计引入氧空位尤其是表面氧空位，以期制备一种集优异的吸附和高效的光催化反应于一体的半导体催化剂，促进污染物去除的整体进程。
一般来说，获得氧空位缺陷的SnO2可以通过使用金属锡和Sn4+之间自发进行的反应将部分四价锡离子还原为二价锡离子。当然，也可使用二价锡为锡源，将其部分氧化为Sn4+，虽然此过程并非热力学有利的反应，但可在SnO2晶格中较大程度的保留Sn2+，以调节氧空位缺陷的浓度。本发明采用Sn2+为锡源，通过低温下的水热过程获得氧空位缺陷的SnO2。首先，氧空位的作用体现在能带结构的调整，使带隙减小到3.16eV从而具备可见光响应能力，导带和价带均有不同程度的上移，增加了导带电子的还原能力。其次，存在于表面的氧空位作为吸附和光催化反应的活性位点，促进在表面发生的传质过程。最后，氧空位还对光生电子和空穴的有效分离发挥作用，可捕获光生电子并延长其寿命。总之，本发明制备的氧空位缺陷的SnO2是一种集优异吸附和光催化反应于一体的光催化剂。
发明内容
本发明的目的在于提供了一种氧空位缺陷的SnO2纳米材料及其在吸附和光催化的应用。本发明通过较低温度下的水热过程在SnO2合成中保留部分Sn2+，获得氧空位浓度可调的SnO2光催化剂，能响应可见光、有效分离光生电子和空穴以及具有优异的吸附能力。该方法操作简单、条件温和、氧空位浓度可调，采用该法制得的氧空位缺陷的SnO2纳米材料应用于污染物去除时，在光照下表现出高效的吸附和降解甲基橙、还原Cr(VI)的能力，证明了该发明的可行性。
为实现上述目的，本发明的技术方案如下：
具体地，本发明的第一方面提供一种氧空位缺陷的SnO2纳米材料的制备方法，其包括以下步骤：
S1、采用水热法制备氧空位缺陷的SnO2纳米材料，以二水二氯化锡(SnCl2·2H2O)为原料，将二水二氯化锡(SnCl2·2H2O)磁力搅拌后溶解于去离子水中获得白色半透明溶液A；
S2、将步骤S1得到的半透明溶液A转移至水热反应釜中并在恒温干燥箱中保温，得到反应物B；
S3、将步骤S2中的反应物B随炉冷却至室温后，离心收集沉淀物，并用水和乙醇洗涤数次，干燥研磨后获得浅黄色粉末即为氧空位缺陷的SnO2纳米材料。
优选地，所述步骤S1中磁力搅拌的时间为60～120min。
优选地，步骤S2中的保温温度为70-90℃，保温时间为10-14h。
优选地，所述步骤S3中干燥温度为40-60℃，干燥时间为10-14h。
本发明的第二方面还提供一种氧空位缺陷的SnO2纳米材料，该氧空位缺陷的SnO2纳米材料由权利要求1所述的方法制备得到。
本发明的第三方面还提供一种氧空位缺陷的SnO2纳米材料的使用方法，该氧空位缺陷的SnO2纳米材料为权利要求5所述的氧空位缺陷的SnO2纳米材料。
优选地，该氧空位缺陷的SnO2纳米材料能够应用于光催化降解甲基橙及Cr(VI)的吸附。
优选地，该氧空位缺陷的SnO2纳米材料能够应用于光催化过程。
优选地，将该氧空位缺陷的SnO2纳米材料按照质量-体积比为1:5-1:6的比例加入到5-10mg/L的甲基橙溶液或15-20mg/L的K2CrO4溶液中，在黑暗条件下搅拌一段时间达到吸附-脱附平衡后，再经光照应用于光催化降解甲基橙和还原Cr(VI)。
与现有技术相比，本发明的有益效果如下：
(1)本发明利用Sn2+为锡源，通过较低温度下的水热过程得以保留部分Sn2+，有目的获得氧空位缺陷的SnO2纳米材料。相比于原始SnO2，引入氧空位后具有更宽的光响应范围、更强的光生电载流子分离能力，展现出优异的吸附活性和光催化活性。在黑暗条件搅拌达到吸附-脱附平衡后，对甲基橙和Cr(VI)具有稳定的吸附能力，分别可达43.4％和78.0％。
(2)本发明的氧空位缺陷的SnO2纳米材料在模拟太阳光照射下，对甲基橙和Cr(VI)具有优异的光催化降解和还原能力，对甲基橙的降解效率在6min高达98.0％，对Cr(VI)的还原效率在4min高达98.3％，由此可以证明，本发明所述的氧空位缺陷的SnO2纳米材料是一种集优异的吸附和光催化活性于一体的光催化剂。
附图说明
图1为原始SnO2和氧空位缺陷的SnO2的XRD图。
图2a为原始SnO2的透射电镜图；
图2b为氧空位缺陷的SnO2的透射电镜图。
图3为原始SnO2和氧空位缺陷的SnO2的电子顺磁共振图。
图4a为原始SnO2和氧空位缺陷的SnO2对甲基橙的吸附效率图；
图4b为原始SnO2和氧空位缺陷的SnO2对甲基橙在模拟太阳光下的降解效率图。
图5a为原始SnO2和氧空位缺陷的SnO2对Cr(VI)的吸附效率图；
图5b为原始SnO2和氧空位缺陷的SnO2对Cr(VI)在模拟太阳光下的还原效率图。
具体实施方式
本发明提供一种氧空位缺陷的SnO2纳米材料的制备方法，其包括以下步骤：
S1、采用水热法制备氧空位缺陷的SnO2纳米材料，以二水二氯化锡(SnCl2·2H2O)为原料，磁力搅拌溶解到去离子水中获得白色半透明溶液；
S2、将上述半透明溶液转移至水热反应釜中并在恒温干燥箱中以一定温度保温一段时间；
S3、随炉冷却至室温后，离心收集沉淀物，并用水和乙醇洗涤数次，干燥研磨后获得浅黄色粉末即为氧空位缺陷的SnO2纳米材料。
本发明还提供一种氧空位缺陷的SnO2纳米材料的使用方法，该氧空位缺陷的SnO2纳米材料由上述方法制备得到。
优选地，该氧空位缺陷的SnO2纳米材料能够应用于光催化降解甲基橙及Cr(VI)的吸附。
优选地，该氧空位缺陷的SnO2纳米材料能够应用于光催化过程。
优选地，将该氧空位缺陷的SnO2纳米材料按照1:5的比例加入到10mg/L的甲基橙溶液或20mg/L的K2CrO4溶液中，在黑暗条件下搅拌一段时间达到吸附-脱附平衡后，再经光照应用于光催化降解甲基橙和还原Cr(VI)。
下面结合具体实施例对本发明的工作原理进行进一步说明：
实施例1：
步骤(1)：采用水热法制备氧空位缺陷的SnO2纳米材料，以二水二氯化锡(SnCl2·2H2O)为原料，将0.76g SnCl2·2H2O加入到70mL去离子水中，磁力搅拌90min，获得白色半透明溶液。
步骤(2)：将上述半透明溶液转移至水热反应釜中并在恒温干燥箱中80℃保温6h。
步骤(3)：随炉冷却至室温后，离心收集沉淀物，并用水和乙醇洗涤数次，干燥研磨后获得浅黄色粉末即为氧空位缺陷的SnO2纳米材料。
图1是实施例1中原始SnO2和氧空位缺陷的SnO2的XRD图，原始SnO2的所有衍射峰均与金红石相(JCPDS，No.77-0452)匹配良好，其中位于26.486°、33.739°和51.563°处的衍射峰分别对应于(110)、(101)和(211)晶面。氧空位缺陷的SnO2的射峰整体上与金红石相SnO2(JCPDS，No.77-0452)对应良好，但其中对应于(101)晶面的衍射峰向小角度发生了偏移，这可能是由于在低温水热过程中部分Sn2+得以保留下来，替代了SnO2晶格中的Sn4+，因为离子半径Sn+(93pm)＞Sn4+(71pm)，因此在Sn2+成功掺杂后，引起晶格畸变使晶格常数变大。这证实了氧空位的成功引入。
图2a和图2b分别是实施例1中原始SnO2和氧空位缺陷的SnO2的透射电镜图，SnO2纳米颗粒的直径约为2～5nm左右，但因颗粒间吸引力存在自聚集的情况。氧空位缺陷的SnO2大部分为纳米尺度的小颗粒，同时也存在类似于纳米片的形貌。
图3是实施例1中原始SnO2和氧空位缺陷的SnO2的电子顺磁共振图，SnO2显示出以g＝2.004为中心的对称信号，而氧空位缺陷的SnO2还观察到以g＝1.987为中心的信号，这可以解释为g＝1.987的ESR信号可能与表面氧空位相关联。
图4a和图4b分别是实施例1中原始SnO2和氧空位缺陷的SnO2对甲基橙的吸附效率图以及在模拟太阳光下的降解效率图。氧空位缺陷的SnO2对甲基橙表现出优异的吸附和光催化降解活性，吸附率为43.4％，降解效率在6min达到了98.0％，远高于原始的SnO2。
图5a和图5b分别是实施例1中原始SnO2和氧空位缺陷的SnO2对Cr(VI)的吸附效率图和在模拟太阳光下还原效率图。氧空位缺陷的SnO2对Cr(VI)表现出优异的吸附和光催化降解活性，吸附率为78.0％，降解效率在4min达到了98.3％，远高于原始的SnO2。证实了氧空位的引入可有效拓宽光响应范围、提升光生载流子的分离能力、促进污染物在表面发生的吸附和氧化还原反应，具有卓越的吸附和光催化活性。
实施例2：
步骤(1)：采用水热法制备氧空位缺陷的SnO2纳米材料，以二水二氯化锡(SnCl2·2H2O)为原料，将0.76g SnCl2·2H2O加入到70mL去离子水中，磁力搅拌60min，获得白色半透明溶液。
步骤(2)和步骤(3)与实施例1中相同。
实施例2得到的氧空位缺陷的SnO2纳米材料在模拟太阳光照射下，对甲基橙的吸附率为47.4％，降解率在6min为62.6％，对Cr(VI)的吸附率为72.5％，降解率在4min为92.6％。
实施例3：
步骤(1)：采用水热法制备氧空位缺陷的SnO2纳米材料，以二水二氯化锡(SnCl2·2H2O)为原料，将0.76g SnCl2·2H2O加入到70mL去离子水中，磁力搅拌120min，获得白色半透明溶液。
步骤(2)和步骤(3)与实施例1中相同。
实施例3得到的氧空位缺陷的SnO2纳米材料在模拟太阳光照射下，对甲基橙的吸附率为45.8％，降解率在6min为68.4％，对Cr(VI)的吸附率为79.8％，降解率在4min为97.4％。
以上所述的实施例仅是对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。
Claims (8)
1.一种氧空位缺陷的SnO2纳米材料的制备方法，其特征在于：其包括以下步骤：
S1、采用水热法制备氧空位缺陷的SnO2纳米材料，以二水二氯化锡(SnCl2·2H2O)为原料，将二水二氯化锡(SnCl2·2H2O)磁力搅拌后溶解于去离子水中获得白色半透明溶液A；
S2、将步骤S1得到的半透明溶液A转移至水热反应釜中并在恒温干燥箱中保温，得到反应物B；
S3、将步骤S2中的反应物B随炉冷却至室温后，离心收集沉淀物，并用水和乙醇洗涤数次，干燥研磨后获得浅黄色粉末即为氧空位缺陷的SnO2纳米材料。
2.根据权利要求1所述的氧空位缺陷的SnO2纳米材料的制备方法，其特征在于：所述步骤S1中磁力搅拌的时间为60～120min。
3.根据权利要求1所述的氧空位缺陷的SnO2纳米材料的制备方法，其特征在于：步骤S2中的保温温度为70-90℃，保温时间为10-14h。
4.根据权利要求1所述的氧空位缺陷的SnO2纳米材料的制备方法，其特征在于：所述步骤S3中干燥温度为40-60℃，干燥时间为10-14h。
5.一种氧空位缺陷的SnO2纳米材料，其特征在于：该氧空位缺陷的SnO2纳米材料由权利要求1所述的方法制备得到。
6.一种氧空位缺陷的SnO2纳米材料的使用方法，其特征在于：该氧空位缺陷的SnO2纳米材料为权利要求5所述的氧空位缺陷的SnO2纳米材料，该氧空位缺陷的SnO2纳米材料能够应用于光催化降解甲基橙及Cr(VI)的吸附。
7.根据权利要求6所述的氧空位缺陷的SnO2纳米材料的使用方法，其特征在于：该氧空位缺陷的SnO2纳米材料能够应用于光催化过程。
8.根据权利要求7所述的氧空位缺陷的SnO2纳米材料的使用方法，其特征在于：将该氧空位缺陷的SnO2纳米材料按照质量-体积比为1:5-1:6的比例加入到5-10mg/L的甲基橙溶液或15-20mg/L的K2CrO4溶液中，在黑暗条件下搅拌一段时间达到吸附-脱附平衡后，再经光照应用于光催化降解甲基橙和还原Cr(VI)。
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