CN108014822A - 一种碘化银/硒酸铋复合材料的制备方法和应用 - Google Patents
一种碘化银/硒酸铋复合材料的制备方法和应用 Download PDFInfo
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- 229910021612 Silver iodide Inorganic materials 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229940045105 silver iodide Drugs 0.000 title claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 19
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
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- 239000000463 material Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
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- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VZCBIMOCFWPJLF-UHFFFAOYSA-N [Se](O)(O)(=O)=O.[Bi] Chemical compound [Se](O)(O)(=O)=O.[Bi] VZCBIMOCFWPJLF-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
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- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
本发明公开了一种碘化银/硒酸铋复合材料的制备方法和应用。采用原位沉积的方法,先将Bi2SeO5粉末分散在去离子水中,随后往上述溶液中加入AgNO3溶液;置于暗处搅拌30 min后逐滴加入KI溶液直至溶液变成亮黄色;离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,真空干燥后在氮氢混合气氛中煅烧即得AgI/Bi2SeO5复合物,颗粒状的AgI沉淀在片状的Bi2SeO5上。本发明反应条件温和,易控制,且制备过程环保无污染,有利于工业化生产;有效克服了以往AgI颗粒在负载过程中颗粒易团聚,或者容易被氧化的问题。所制备的复合材料具有较好的光催化活性,能有效地对有污染物进行光降解和选择性有机合成。
Description
技术领域
本发明属于光催化复合材料制备技术领域,具体涉及一种碘化银/硒酸铋复合材料的制备方法和应用。
背景技术
银基半导体光催化材料的禁带宽度比较低,在可见光区有较强的感光度,同时人们发现其也具有很好的光催化活性,因此引起了人们的广泛关注和深入研究,如AgX(X=C1,Br,I)、Ag2S、Ag@AgX(X=C1,Br,I)、Ag3P04, Ag3As04、Ag2M04(M=Cr,Mo,W)等。但由于其不稳定,见光易分解出单质银,不能作为单独的光催化剂使用。另一方面是银基半导体材料光生电子空穴对复合率较高,导致光生载流子的利用率不高。因此人们研究将其与半导体材料复合,用以提高系统的电荷分离效率,扩展其对光谱的吸收范围,最终用于改性半导体催化剂的光催化活性。
目前,有许多关于半导体复合改性光催化剂的研究已见于报道。Zhang等人通过原位沉淀法制得暴露(100)晶面的Bi2SiO5/AgI光催化剂,成功将Bi2SiO5的光响应范围拓展到可见光范围,且相比于单一的Bi2SiO5和AgI光催化剂,复合后的光催化剂具有更显著的可见光降解酸性红G水溶液的性能(Journal of Materials Chemistry A 2015,3,16737-16745)。黄柏标课题组成功合成出Ag/AgBr/BiOBr复合光催化剂,复合材料的光吸收性能显示其具有等离子体效应,且其在光催化杀菌和染料降解反应中均展现出较高的光催化活性(Chemical Communications, 2011, 47, 7054-6)。
中国发明专利ZL201510703173.4公开了在紫外光照射下,Bi2SeO5光催化剂不仅具有降解污染物的广谱性,且在光催化有机合成方面也有一定效果。然而,由于Bi2SeO5属于宽带隙的半导体材料,禁带宽度在3.5 eV,故其只能吸收紫外光。众所周知,波长低于400 nm的紫外光部分约占太阳光总能量的5%,使得95%的太阳光不能被有效利用,很大程度上制约了Bi2SeO5在环境治理方面的实际应用。同时该专利中的Bi2SeO5光催化剂制备过程需要先合成出Bi2Se3前驱体,再通过氧化处理得到Bi2SeO5。这个过程步骤较多,在实际生产中可能出现一定的不可控行。因此急需进一步开发新型的简单的制备方法。
另一方面,具有大比表面积的Bi2SeO5纳米片作为催化剂载体,通过与银基光催化剂的复合,能够有效吸附有机污染物并促进复合材料光生电子空穴对的分离,从而有利于有机污染物在可见光下的光催化降解,拓展了Bi2SeO5与银基复合光催化材料在光催化领。
发明内容
本发明的目的是为解决现有技术的不足,提供一种对可见光响应的碘化银/硒酸铋复合光催化剂的制备方法和应用。本发明所制备的复合光催化剂具有催化活性高、操作方便、易回收等优点。
为实现上述目的,本发明采用如下技术方案:
一种对碘化银/硒酸铋复合材料的制备方法,是通过原位沉积法制得,具体包括以下步骤:
(1)将2 mmol氧化铋、3 mmol硒粉和0.5 g硼氢化钠混合均匀后置于马弗炉中,在空气气氛下,于500 ℃条件下煅烧3 h,得到的固体样品即为Bi2SeO5;
(2)称取0.40 mmol Bi2SeO5粉末分散在25 mL的去离子水中,随后往所得溶液中加入10 mL AgNO3溶液,置于暗处搅拌30 min后逐滴加入25 mL KI溶液直至溶液变成亮黄色;其中,AgNO3和KI的加入量是2-20 μmol,且加入的AgNO3和KI的摩尔量为1:1;随后离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,60 ℃真空干燥2 h即得到碘化银/硒酸铋(AgI/Bi2SeO5)复合物前驱体;
(3)将碘化银/硒酸铋复合物前驱体于氢气含量为0.5-20v/v%的氮氢混合气中,于200-500 ℃煅烧0.5-4 h后,即制得所述碘化银/硒酸铋(AgI/Bi2SeO5)复合材料;所制得的AgI/Bi2SeO5复合材料中,AgI的摩尔百分比为0.5-5%。
所得碘化银/硒酸铋复合材料可用于光催化降解污染物和选择性有机合成;具体的,所述碘化银/硒酸铋复合材料用于光催化降解染料罗丹明B和可见光下选择性催化氧化苯甲醇至苯甲醛。
本发明的显著优点在于:
1、本发明利用氧化铋、硒粉和硼氢化钠三者在500 ℃,空气气氛条件下煅烧3 h的相互作用下,一步法直接合成出硒酸铋,克服了以往硒酸铋合成过程中需要多步的问题;
2、本发明利用原位沉积法结合在还原气氛下热退火将AgI颗粒均匀的负载于Bi2SeO5片上,反应条件温和,易控制,且制备过程环保无污染,有利于工业化生产;有效克服了以往AgI颗粒在负载过程中颗粒易团聚,或者容易被氧化的问题;同时热退火过程有效的出尽了促进了AgI和Bi2SeO5的紧密作用,提升其协同性能;
3、本发明采用AgI对Bi2SeO5对进行负载,在一定程度上解决了AgI和Bi2SeO5作为单一光催化剂分别存在稳定性差和不可吸收可见光的缺点,充分利用了两种材料分别可以吸收可见光和高稳定性的优点,从而集中有效地对有污染物进行光降解和选择性有机合成。
附图说明
图1为Bi2SeO5、AgI及AgI/Bi2SeO5不同摩尔比的X射线粉末衍射谱图;
图2为Bi2SeO5、AgI及AgI/Bi2SeO5样品的扫描电镜图;
图3为Bi2SeO5、AgI及不同复合比例AgI/Bi2SeO5样品在可见光下选择性氧化苯甲醇活性图;
图4为Bi2SeO5、AgI及不同复合比例AgI/Bi2SeO5样品在可见光(λ≥400 nm)下降解RhB的活性比较图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
(1)光催化剂Bi2SeO5的制备:将2 mmol氧化铋,3 mmol硒粉和0.5 g硼氢化钠混合均匀后置于马弗炉中,在空气气氛下,于500 ℃条件下煅烧3 h,即可;
(2)复合光催化剂AgI/Bi2SeO5的制备:采用原位沉积的方法制备AgI的摩尔百分比为0.5%的AgI/Bi2SeO5复合物,称取0.40 mmol Bi2SeO5粉末分散在25 mL的去离子水中,随后往所得溶液中加入10 mL AgNO3溶液(含2 μmol AgNO3);置于暗处搅拌30 min后逐滴加入25mL含2 μmol KI的溶液直至溶液变成亮黄色;离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,60 ℃真空干燥2 h即得到AgI/Bi2SeO5复合物前驱体;所得前驱体于氢气含量为0.5v/v%的氮氢混合气中200 ℃煅烧0.5 h后即可得到AgI/Bi2SeO5复合物;所得样品记为A/B-0.5。
实施例2
(1)光催化剂Bi2SeO5的制备:将2 mmol氧化铋,3 mmol硒粉和0.5 g硼氢化钠混合均匀后置于马弗炉中,在空气气氛下,于500 ℃条件下煅烧3 h,即可;
(2)复合光催化剂AgI/Bi2SeO5的制备:采用原位沉积的方法制备AgI的摩尔百分比为0.7%的AgI/Bi2SeO5复合物,称取0.40 mmol Bi2SeO5粉末分散在25 mL的去离子水中,随后往所得溶液中加入10 mL AgNO3溶液(含2.8 μmol AgNO3);置于暗处搅拌30 min后逐滴加入25 mL 含2.8 μmol KI的溶液直至溶液变成亮黄色;离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,60 ℃真空干燥2 h即得到AgI/Bi2SeO5复合物前驱体;所得前驱体于氢气含量为20v/v%的氮氢混合气中500 ℃煅烧0.5 h后即可得到AgI/Bi2SeO5复合物;所得样品记为A/B-0.7。
实施例3
(1)光催化剂Bi2SeO5的制备:将2 mmol氧化铋,3 mmol硒粉和0.5 g硼氢化钠混合均匀后置于马弗炉中,在空气气氛下,于500 ℃条件下煅烧3 h,即可;
(2)复合光催化剂AgI/Bi2SeO5的制备:采用原位沉积的方法制备AgI的摩尔百分比为1%的AgI/Bi2SeO5复合物,称取0.40 mmol Bi2SeO5粉末分散在25 mL的去离子水中,随后往所得溶液中加入10 mL AgNO3溶液(含4 μmol AgNO3);置于暗处搅拌30 min后逐滴加入25mL 含4 μmol KI的溶液直至溶液变成亮黄色;离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,60 ℃真空干燥2 h即得到AgI/Bi2SeO5复合物前驱体;所得前驱体于氢气含量为10v/v%的氮氢混合气中300 ℃煅烧4 h后即可得到AgI/Bi2SeO5复合物;所得样品记为A/B-1。
实施例4
(1)光催化剂Bi2SeO5的制备:将2 mmol氧化铋,3 mmol硒粉和0.5 g硼氢化钠混合均匀后置于马弗炉中,在空气气氛下,于500 ℃条件下煅烧3 h,即可;
(2)复合光催化剂AgI/Bi2SeO5的制备:采用原位沉积的方法制备AgI的摩尔百分比为2%的AgI/Bi2SeO5复合物,称取0.40 mmol Bi2SeO5粉末分散在25 mL的去离子水中,随后往所得溶液中加入10 mL AgNO3溶液(含8 μmol AgNO3);置于暗处搅拌30 min后逐滴加入25mL 含8 μmol KI的溶液直至溶液变成亮黄色;离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,60 ℃真空干燥2 h即得到AgI/Bi2SeO5复合物前驱体;所得前驱体于氢气含量为10v/v%的氮氢混合气中200 ℃煅烧4 h后即可得到AgI/Bi2SeO5复合物;所得样品记为A/B-2。
实施例5
(1)光催化剂Bi2SeO5的制备:将2 mmol氧化铋,3 mmol硒粉和0.5 g硼氢化钠混合均匀后置于马弗炉中,在空气气氛下,于500 ℃条件下煅烧3 h,即可;
(2)复合光催化剂AgI/Bi2SeO5的制备:采用原位沉积的方法制备AgI的摩尔百分比为5%的AgI/Bi2SeO5复合物,称取0.40 mmol Bi2SeO5粉末分散在25 mL的去离子水中,随后往所得溶液中加入10 mL AgNO3溶液(含20 μmol AgNO3);置于暗处搅拌30 min后逐滴加入25mL 含20 μmol KI的溶液直至溶液变成亮黄色;离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,60 ℃真空干燥2 h即得到AgI/Bi2SeO5复合物前驱体;所得前驱体于氢气含量为0.5v/v%的氮氢混合气中200 ℃煅烧0.5 h后即可得到AgI/Bi2SeO5复合物。
图1为Bi2SeO5、AgI及AgI/Bi2SeO5复合样品的X射线粉末衍射谱图。由图可知,AgI/Bi2SeO5系列样品的XRD图中均可观察到前驱体Bi2SeO5(JCPDS 70-5102)的衍射峰,表明AgI复合并未改变Bi2SeO5原有的晶型结构。值得注意的是,AgI/Bi2SeO5系列样品在2θ值为23.7°,39.2 °,46.3 °和22.3 °处有四个特征峰,分别归属于AgI的(111),(220),(311)和(100)晶面,表明AgI已成功修饰在Bi2SeO5上。同时, AgI/Bi2SeO5复合样品中AgI特征峰强度随着复合量的增加而增强。
图2是Bi2SeO5、AgI和A/B-1的扫描电镜图。从图2中的a中可以看出,纯相的Bi2SeO5呈现的是大小约为4 μm的纳米花形貌,表面较光滑平整;而纯的AgI呈现颗粒状,团聚相对较严重(图2中的b)。Bi2SeO5与AgI按照摩尔比1:1复合之后的扫描电镜如图2中的c所示,可以观察到AgI复合后Bi2SeO5样品纳米花的形貌并未改变,纳米花瓣的层与层之间散落着许多大小相对均一的AgI颗粒,表明Bi2SeO5与AgI相互之间复合较紧密。
选择性氧化苯甲醇
采用苯甲醇选择性氧化作为探针反应来进一步研究所合成AgI/Bi2SeO5复合物样品的光催化性能。图3为Bi2SeO5、AgI及不同复合比例AgI/Bi2SeO5样品的选择性氧化苯甲醇活性图,实验结果显示,在仅有光照而不加光催化剂时反应体系中并未有苯甲醛的生成,因此,催化剂的光催化活性可排除苯甲醇自身的催化转化。Bi2SeO5在可见光的照射下几乎没有选择性氧化苯甲醇的活性,而AgI在光照下苯甲醇的转化率也仅为6.8%。AgI/Bi2SeO5复合样品选择性氧化苯甲醇的选择性优异,均可将苯甲醇转化为苯甲醛,而并未有其他物质生成,选择性均达到99.9%,且其活性随AgI复合量的增加呈现出先增加后减小的趋势,当AgI与Bi2SeO5复合的摩尔比为1:1时,样品的活性最佳,转化率为17.8%,相比于AgI提高了大约3倍,继续增大AgI的复合量,其转化率下降。
降解染料罗丹明B
图4为Bi2SeO5、AgI及不同复合比例AgI/Bi2SeO5样品在可见光(λ≥400 nm)下光催化降解RhB的活性图。反应体系均先在暗态下达到吸脱附平衡后开始光照,由图可知,可以忽略RhB自身的光分解。Bi2SeO5在可见光的照射下几乎没有光催化降解RhB的性能,而AgI经40min可见光照射后对RhB的降解率约为20%。值得注意的是, Bi2SeO5复合AgI后其光催化性能明显提高,当二者的摩尔比为1:1时,光催化降解RhB的效果达到最佳,经40 min光照后,对RhB的去除率高达100%。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种碘化银/硒酸铋复合材料的制备方法,其特征在于:具体包括以下步骤:
(1)将2 mmol氧化铋、3 mmol硒粉和0.5 g硼氢化钠混合均匀后置于马弗炉中,在空气气氛下,于500 ℃条件下煅烧3 h,得到的固体样品即为Bi2SeO5;
(2)称取0.40 mmol Bi2SeO5粉末分散在25 mL的去离子水中,随后往所得溶液中加入10mL AgNO3溶液,置于暗处搅拌30 min后逐滴加入25 mL KI溶液直至溶液变成亮黄色;离心分离,沉淀物分别用蒸馏水和无水乙醇洗涤,60 ℃真空干燥2 h即得到碘化银/硒酸铋复合物前驱体;
(3)将碘化银/硒酸铋复合物前驱体于氢气含量为0.5-20v/v%的氮氢混合气中,于200-500 ℃煅烧0.5-4 h后即制得所述碘化银/硒酸铋复合材料。
2.根据权利要求1所述的碘化银/硒酸铋复合材料的制备方法,其特征在于:所制得的碘化银/硒酸铋复合材料中,碘化银的摩尔百分比为0.5-5%。
3.根据权利要求1所述的碘化银/硒酸铋复合材料的制备方法,其特征在于:步骤(2)中, AgNO3和KI的加入量为2-20 μmol,且AgNO3和KI的摩尔比为1:1。
4.一种如权利要求1~3中任一项所述的制备方法制得的碘化银/硒酸铋复合材料的应用,其特征在于:所述碘化银/硒酸铋复合材料用于光催化降解污染物和选择性有机合成。
5.根据权利要求4所述的应用,其特征在于:所述碘化银/硒酸铋复合材料用于光催化降解染料罗丹明B和可见光下选择性催化氧化苯甲醇至苯甲醛。
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CN112452343A (zh) * | 2020-09-15 | 2021-03-09 | 湖北省工程咨询股份有限公司 | 一种AgI-Sb2O3复合光催化剂及其制备方法和应用 |
CN112526135A (zh) * | 2021-02-05 | 2021-03-19 | 山东理工大学 | 一种检测前列腺特异性抗原的光电化学生物传感器的制备方法及应用 |
CN115888767A (zh) * | 2022-11-04 | 2023-04-04 | 电子科技大学长三角研究院(湖州) | 一种碳负载缺陷态硒酸铋异质结光催化剂及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102513135A (zh) * | 2011-12-30 | 2012-06-27 | 温州大学 | 一种BiOI/AgX可见光响应光催化剂及其制备方法和应用 |
CN104492464A (zh) * | 2015-01-09 | 2015-04-08 | 江苏大学 | 一种碘化银/β型氧化铋复合材料的制备方法 |
CN105195180A (zh) * | 2015-10-27 | 2015-12-30 | 福州大学 | 一种新型硒酸铋光催化剂及其制备方法与应用 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN104492464A (zh) * | 2015-01-09 | 2015-04-08 | 江苏大学 | 一种碘化银/β型氧化铋复合材料的制备方法 |
CN105195180A (zh) * | 2015-10-27 | 2015-12-30 | 福州大学 | 一种新型硒酸铋光催化剂及其制备方法与应用 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112452343A (zh) * | 2020-09-15 | 2021-03-09 | 湖北省工程咨询股份有限公司 | 一种AgI-Sb2O3复合光催化剂及其制备方法和应用 |
CN112452343B (zh) * | 2020-09-15 | 2023-04-18 | 湖北省工程咨询股份有限公司 | 一种AgI-Sb2O3复合光催化剂及其制备方法和应用 |
CN112526135A (zh) * | 2021-02-05 | 2021-03-19 | 山东理工大学 | 一种检测前列腺特异性抗原的光电化学生物传感器的制备方法及应用 |
CN115888767A (zh) * | 2022-11-04 | 2023-04-04 | 电子科技大学长三角研究院(湖州) | 一种碳负载缺陷态硒酸铋异质结光催化剂及其制备方法 |
CN115888767B (zh) * | 2022-11-04 | 2024-03-15 | 电子科技大学长三角研究院(湖州) | 一种碳负载缺陷态硒酸铋异质结光催化剂及其制备方法 |
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