CN108067279A - 纳米复合材料、其制备方法及其应用 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 26
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000007146 photocatalysis Methods 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
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- 239000012467 final product Substances 0.000 claims abstract 2
- 239000004615 ingredient Substances 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 229910015667 MoO4 Inorganic materials 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 3
- 229960000502 poloxamer Drugs 0.000 claims description 3
- 229920001983 poloxamer Polymers 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229910015221 MoCl5 Inorganic materials 0.000 claims description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims 1
- 229910000397 disodium phosphate Inorganic materials 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 10
- NDYNABNWLRVCDO-UHFFFAOYSA-N phosphoric acid silver Chemical compound [Ag].P(O)(O)(O)=O NDYNABNWLRVCDO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
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- 229910002804 graphite Inorganic materials 0.000 description 3
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- 238000000034 method Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical class [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明涉及一种纳米复合材料纳米复合材料、其制备方法及其用途，该复合材料为三元纳米复合物，其中增强相为碳氮烯、钼酸银，基础成分为Ag3PO4，其中碳氮烯的质量百分含量为2％～12％，钼酸银的质量百分含量为10％‑20％，余量为Ag3PO4。将固相烧结合成的g‑C3N4均匀分散到银氨溶液中形成碳氮烯‑银氨混合溶液；采用滴加的方式引入磷酸盐、钼源与表面活性剂的混合溶液，常温反应2‑4h，用去离子水、无水乙醇反复清洗产物，干燥、即得。提升磷酸银基复合光催化材料的光催化性能及稳定性，产率高，拓展其在光催化处理工业废水及光催化分解水产氧等领域的应用。
Description
技术领域
本发明涉及纳米材料领域，具体地，是一种碳氮烯、钼酸银共修饰磷酸银复合物、其制备方法及其作为纳米光催化剂的用途。
背景技术
磷酸银(Ag3PO4)作为银基光催化材料典型代表，由于具有较窄的带隙能量、较强的可见光吸收能力和明显的可见光光催化活性，因而被作为利用太阳能进行境净化和能源清洁生产的最有潜力的光催化剂之一。然而Ag3PO4微溶于水及稳定性较差的特点抑制了其广泛的应用，因此发展高稳定性与高性能的 Ag3PO4基复合光催化材料是当前光催化领域研究的热点。
目前，Ag3PO4基复合光催化材料以二元复合材料为主，如引入g-C3N4，利用其合适的带隙结构和本身的类石墨结构来提高Ag3PO4的光催化性能，同时 g-C3N4与Ag3PO4存在合适的能带匹配结构，通过两者的复合可以提高光生电子空穴的分离效率，进而提高其光催化性能。
公开号为CN103464191A的中国专利文件，报道一种石墨型氮化碳酸银复合光催化材料及其制备方法，其对有机染料具有较好降解作用。此外，银基光催化材料中的固溶体复合，可以利用固溶体效应来调节价带和导带的电势位置，从而进一步提升复合材料的光催化性能。
Ag2MoO4作为新颖的银基光催化材料，在近期受到了广泛的关注，大量的文献证明了其优异的性能。公开号为CN105771988A的中国专利文件报道了一种高催化活性分等级结构钼酸银的制备方法。公开号为CN105728010A的中国专利文件报道了一种抗菌钼酸银石墨相氮化碳复合可见光催化剂的制备方法，表明了其在光催化领域的应用前景。发明人也成功合成了Ag3PO4/Ag2MoO4固溶体，光催化实验也证明其对有机染料具有很好的降解作用，这些成果已发表在催化学报(Chinese Journal of Catalysis 38(2017)337–347)。
发明内容
针对现有技术的不足，本发明的目的之一在于提供一种复合纳米材料，采用碳氮烯、钼酸银共修饰磷酸银，形成三元增强复合光催化剂，提升磷酸银基复合光催化材料的光催化性能及稳定性，产率高，拓展其在光催化处理工业废水及光催化分解水产氧等领域的应用。
本发明的另一个目的在于提供一种复合纳米材料的制备方法，成本低廉、工艺简单。
本发明的另一个目的在于提供一种复合纳米材料用作光催化剂的用途。
上述目的是通过如下技术方案实现的：
一种纳米复合材料，为三元纳米复合物，其中增强相为碳氮烯 (g-C3N4)、钼酸银，基础相为Ag3PO4，钼酸银与磷酸银颗粒均匀的生长在g-C3N4纳米片表面；其中碳氮烯的质量百分含量为2％～ 12％，钼酸银的质量百分含量为10％-20％，余量为Ag3PO4；
具体而言，生长在g-C3N4纳米片表面的磷酸银颗粒为微米级，而钼酸银为纳米级的颗粒。
纳米复合材料的制备方法，步骤如下：
(1)碳氮烯-银氨混合溶液的配制：将固相烧结合成的g-C3N4均匀分散到银氨溶液中形成碳氮烯-银氨混合溶液；
其中碳氮烯的添加量为1-4g/L；
银氨溶液中Ag+的前体为AgNO3，浓度为1-2mol/L,氨水质量浓度为10％-20％；
分散条件：避光搅拌6-10h；
(2)碳氮烯-银氨/钼酸银/磷酸银的合成：向步骤(1)的反应液中采用滴加的方式引入磷酸盐、钼源与表面活性剂的混合溶液，常温反应2-4h，用去离子水、无水乙醇反复清洗产物，干燥后得到反应产物。
步骤(2)中磷酸盐为Na2HPO4、NaH2PO4或者NH4H2PO4，其添加量为0.3-0.8mol/L；
钼源为MoO3、(NH4)2MoO4或MoCl5，其添加量为0.1-0.2 mol/L；
表面活性剂为聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、聚乙二醇或者泊洛沙姆；其中聚乙烯吡咯烷酮或十六烷基三甲基溴化铵作为表面活性剂的添加量为0.5g/L-5g/L；聚乙二醇或者泊洛沙姆作为表面活性剂的添加量为0.2g/L-2g/L。
上述的纳米复合材料作为光催化剂，应用于能源领域，如光催化分解水产氧；环境保护领域，如有机废水中有机染料、酚类、抗生素、重金属离子的降解及空气中有机污染物的降解，增强相 Ag2MoO4和g-C3N4的加入，产氧效率为纯Ag3PO4的2-3倍，且光催化分解水产氧的能力随时间的延长而增强。
本发明采用简易的工艺合成高光催化性能石墨烯/钼酸银/磷酸银纳米复合材料，所得复合纳米材料对工业废水中的酚类与抗生素具有很好的降解效率，40min内的降解率可达60％以上；应用于光催化分解水产氧时，其产氧效率为纯Ag3PO4的2-3倍，光催化时间为0.5-1h,因此在光催化、气敏、污水处理等领域中具有重要的应用，有望用于大规模的工业生产。
附图说明
图1a为纯g-C3N4、纯Ag3PO4、Ag2MoO4和实施例1-3的不同g-C3N4含量的g-C3N4/Ag2MoO4/Ag3PO4复合材料的XRD图谱，从图中可以看出，纯Ag3PO4和Ag2MoO4的衍射峰与分别与立方相Ag3PO4的标准卡片PDF#06-0505和立方相Ag2MoO4的标准卡片PDF#08-0473相一致，并且都具有良好的结晶性能。纯 g-C3N4在2θ角度27.4°出现一个强特征峰，对应六方相g-C3N4的(002)晶面 (JCPDS NO.87-1526)。在g-C3N4/Ag2MoO4/Ag3PO4复合光催化剂XRD图谱中，Ag3PO4特征衍射峰的位置没有发生变化，然而我们并没有发现纯g-C3N4和 Ag2MoO4的特征衍射峰，这主要是由于g-C3N4和Ag2MoO4含量较低。图1b是氧化石墨烯/钼酸银/磷酸银复合物的XPS全谱图，进一步证明了样品中Ag、 C、N、P、Mo、O元素的存在，进一步证实g-C3N4、Ag3PO4及Ag2MoO4三元复合材料的形成。
图2为碳氮烯/钼酸银/磷酸银复合材料的投射电镜图(TEM)，可以看出钼酸银与磷酸银颗粒均匀的生长在g-C3N4纳米片表面，其中微米级的颗粒为磷酸银，而钼酸银为纳米级的颗粒。
图3为本发明制得的碳氮烯/钼酸银/磷酸银复合光催化剂降解酚类与抗生素曲线，由图可知，可见光条件下，碳氮烯/钼酸银/磷酸银对苯酚与四环素都具有很好的降解效果，在40min内分解降解58％和75％。
图4为纯Ag3PO、Ag2MoO4和g-C3N4/Ag2MoO4/Ag3PO4复合材料光催化分解水产氧的能力随时间变化的曲线图。从图中可以看出，在50min的光照后，纯Ag2MoO4与纯Ag3PO4产氧量均较低，约为7umol·L-1和16umol·L-1，而在三元体系中，随着Ag2MoO4和g-C3N4的加入，产氧量得到进一步提升，产氧量最高可达39 umol·L-1，是纯Ag3PO4产氧量的2.4倍。
具体实施方式
以下通过具体实施方式进一步描述本发明，由技术常识可知，本发明也可通过其它的不脱离本发明技术特征的方案来描述，因此所有在本发明范围内或等同本发明范围内的改变均被本发明包含。
本发明所采用的所有试剂均为商业产品，可经过市售途径获得。
实施例1：
(1)将10％氨水溶液逐滴滴加到40mL、浓度为2mol/L的AgNO3溶液中，得到银氨溶液；
将0.09g g-C3N4加入上述银氨溶液，避光的条件下持续搅拌10h后形成石墨烯-银氨混合溶液；
(2)0.01mol NaH2PO4与0.0012mol Na2MoO4溶于50mL的去离子水中，超声1h后形成混合液，再将十六烷基三甲基溴化铵1g 加入该溶液，继续磁力搅拌3h。在保持磁力搅拌的条件下，将上述溶液逐滴滴加到步骤(1)的石墨烯-银氨混合溶液中，控制滴加速度2s/滴。待反应完全后，继续搅拌6h,将所获得的墨绿色沉淀物用乙醇和去离子水反复洗涤离心，最后将样品放于60℃真空干燥箱中过夜干燥8h，其产率为96％，其中g-C3N4的含量为2％，钼酸银为10％，余量磷酸银。整个反应过程与干燥过程均保持在避光条件下进行。
实施例2：
(1)将10％氨水溶液逐滴滴加到50mL的AgNO3溶液中，其浓度为1mol/L，再将0.42g石墨烯加入上述溶液，避光的条件下持续搅拌10h后形成石墨烯-银氨混合溶液。
(2)0.01mol(NH4)2HPO4与0.002mol(NH4)2MoO4溶于50mL 的去离子水中，超声1h后形成混合液，再将聚乙二醇0.4g加入上述溶液，继续磁力搅拌3h。在保持磁力搅拌的条件下，将上述溶液逐滴滴加到溶液(1)中，控制滴加速度3滴/s。待反应完全后，继续搅拌6h,将所获得的墨绿色沉淀物用乙醇和去离子水反复洗涤离心，最后将样品放于60°真空干燥箱中过夜干燥8h，其产率为92％，其中石墨烯的含量为10％，钼酸银为10％，余量磷酸银。整个反应过程与干燥过程均保持在避光条件下进行。
实施例3：
(1)将10％氨水溶液逐滴滴加到60mL的AgNO3溶液中，其浓度为1mol/L，再将石墨烯0.73g加入上述溶液，避光的条件下持续搅拌10h后形成石墨烯-银氨混合溶液。
(2)0.01molNa2HPO4与0.003mol MoO3溶于50mL的去离子水中，超声1h后形成混合液，再将聚乙烯吡咯烷酮0.5g加入上述溶液，继续磁力搅拌3h。在保持磁力搅拌的条件下，将上述溶液逐滴滴加到溶液(1)中，控制滴加速度2滴/s。待反应完全后，继续搅拌 6h,将所获得的墨绿色沉淀物用乙醇和去离子水反复洗涤离心，最后将样品放于 60°真空干燥箱中过夜干燥8h，其产率为95％，其中石墨烯的含量为1％，钼酸银为25％，余量磷酸银。整个反应过程与干燥过程均保持在避光条件下进行。
Claims (5)
1.一种纳米复合材料，其特征在于为三元纳米复合物，其中增强相为碳氮烯、钼酸银，基础成分为Ag3PO4，其中碳氮烯的质量百分含量为2％～12％，钼酸银的质量百分含量为10％-20％，余量为Ag3PO4；钼酸银与磷酸银颗粒均匀的生长在g-C3N4纳米片表面。
2.权利要求1所述的纳米复合材料的制备方法，其特征在于，包括如下步骤：
(1)碳氮烯-银氨混合溶液的配制：将固相烧结合成的g-C3N4均匀分散到银氨溶液中形成碳氮烯-银氨混合溶液；
其中碳氮烯的添加量为1-4g/L；
银氨溶液中Ag+的前体为AgNO3,浓度为1-2mol/L；
氨水质量浓度为10％-20％；
分散条件：避光搅拌6-10h；
(2)碳氮烯-银氨/钼酸银/磷酸银的合成：向步骤(1)的反应液中采用滴加的方式引入磷酸盐、钼源与表面活性剂的混合溶液，常温反应2-4h，用去离子水、无水乙醇反复清洗产物，干燥、即得。
3.根据权利要求2所述的纳米复合材料的制备方法，其特征在于步骤(2)中磷酸盐为Na2HPO4、NaH2PO4或者NH4H2PO4，其添加量为0.3-0.8mol/L；钼源为MoO3、Na2MoO4或MoCl5，其添加量为0.1-0.2mol/L。
4.根据权利要求2所述的纳米复合材料的制备方法，其特征在于步骤(2)中所述表面活性剂为聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、聚乙二醇或者泊洛沙姆，聚乙烯吡咯烷酮或十六烷基三甲基溴化铵作为表面活性剂的添加量为0.5g/L-5g/L，聚乙二醇或者泊洛沙姆作为表面活性剂的添加量为0.2g/L-2g/L。
5.权利要求1所述的纳米复合材料用作光催化剂的用途，增强相Ag2MoO4和g-C3N4的加入，产氧效率为纯Ag3PO4的2-3倍，且光催化分解水产氧的能力随时间的延长而增强。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929925A (zh) * | 2020-07-13 | 2022-01-14 | 中国石油化工股份有限公司 | 一种自组装纳米粒子复合材料及其制备方法和应用 |
| CN115090307A (zh) * | 2022-08-08 | 2022-09-23 | 国能南京电力试验研究有限公司 | 一种磷酸银复合光催化剂及其制备方法 |
| CN117210080A (zh) * | 2023-10-19 | 2023-12-12 | 青岛中氟氟碳材料有限公司 | 一种高铁内壁用防污染水性涂料的制备方法及应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464191A (zh) * | 2013-09-29 | 2013-12-25 | 天津工业大学 | 石墨型氮化碳磷酸银复合光催化材料及其制备方法 |
-
2017
- 2017-11-03 CN CN201711068147.4A patent/CN108067279A/zh active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464191A (zh) * | 2013-09-29 | 2013-12-25 | 天津工业大学 | 石墨型氮化碳磷酸银复合光催化材料及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| HUA TANG等: "Construction of Ag3PO4/Ag2MoO4 Z-scheme heterogeneous photocatalyst for the remediation of organic pollutants", 《CHINESE JOURNAL OF CATALYSIS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929925A (zh) * | 2020-07-13 | 2022-01-14 | 中国石油化工股份有限公司 | 一种自组装纳米粒子复合材料及其制备方法和应用 |
| CN113929925B (zh) * | 2020-07-13 | 2023-08-15 | 中国石油化工股份有限公司 | 一种自组装纳米粒子复合材料及其制备方法和应用 |
| CN115090307A (zh) * | 2022-08-08 | 2022-09-23 | 国能南京电力试验研究有限公司 | 一种磷酸银复合光催化剂及其制备方法 |
| CN117210080A (zh) * | 2023-10-19 | 2023-12-12 | 青岛中氟氟碳材料有限公司 | 一种高铁内壁用防污染水性涂料的制备方法及应用 |
| CN117210080B (zh) * | 2023-10-19 | 2024-03-29 | 青岛中氟氟碳材料有限公司 | 一种高铁内壁用防污染水性涂料的制备方法及应用 |
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