CN115254084A - 黑色材料负载金属纳米颗粒的复合催化剂的制备方法及应用 - Google Patents
黑色材料负载金属纳米颗粒的复合催化剂的制备方法及应用 Download PDFInfo
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- CN115254084A CN115254084A CN202210146069.XA CN202210146069A CN115254084A CN 115254084 A CN115254084 A CN 115254084A CN 202210146069 A CN202210146069 A CN 202210146069A CN 115254084 A CN115254084 A CN 115254084A
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- Prior art keywords
- composite catalyst
- titanium dioxide
- salt
- black
- black material
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 45
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- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
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- 239000000575 pesticide Substances 0.000 claims description 3
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
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- 229960003405 ciprofloxacin Drugs 0.000 description 6
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- 229910052724 xenon Inorganic materials 0.000 description 6
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- 229910000863 Ferronickel Inorganic materials 0.000 description 5
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 5
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- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 5
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- 235000003891 ferrous sulphate Nutrition 0.000 description 4
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
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- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
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- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F2101/00—Nature of the contaminant
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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
- C02F2101/00—Nature of the contaminant
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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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- C—CHEMISTRY; METALLURGY
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
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Abstract
本发明公开了一种黑色材料负载金属纳米颗粒的复合催化剂的制备方法及其在光催化处理废水中的应用，该方法所制备的黑色材料包括黑色二氧化钛或硫化钼纳米花，均具有显著的可见光吸收能力；本发明所制备的复合材料中金属纳米颗粒表面形成的钝化层可作为优良的半导体，在光催化领域有理想的应用前景；本发明所制备的复合材料对抗生素等具有强吸附、还原和光降解能力；本发明方法具有制备简单、成本低、纳米颗粒分散性好、降解效率高等特点。
Description
技术领域
本发明涉及一种新型黑色材料负载金属纳米颗粒的复合催化剂的制备方法，及该材料应用于光降解抗生素废水、重金属废水、染料废水、农药废水，属于环境功能材料及水处理技术领域。
背景技术
抗生素作为一类新兴的药品及个人护理用品，被广泛使用于医疗业和养殖业。然而，大量研究表明，生物体无法完全吸收所摄入的抗生素，导致残余抗生素被排放进入自然环境中，产生抗性菌和抗性基因。它们的累积一方面对人体健康构成严重威胁，另一方面对动植物体产生毒性，不利于生态系统的平衡发展。显然，抗生素的高效降解具有重要的环境意义。以纳米零价铁为代表的纳米颗粒及其复合材料具有还原性强、环境友好等优点，被广泛研究用于环境修复及污水处理等领域。然而，纳米铁等颗粒的固有磁性导致其易于团聚，可反应位点数量减少，同时，其与目标污染物反应过程中产生致密钝化层，严重阻碍了其与目标污染物的进一步接触，不利于降解反应的进行。
载体负载可通过静电斥力及限域效应改善纳米零价铁的分散性，是一种理想的改性纳米零价铁的方法。研究表明，纳米零价铁钝化层的主要成分为氧化铁，而氧化铁常被作为光催化领域的一种理想半导体。此外，二氧化钛作为一种被广泛使用的光催化剂，具有良好的光反应性及稳定性。然而，二氧化钛的吸光范围仅在紫外区域，导致其光利用能力严重受限。黑色二氧化钛的制备是一种改善普通二氧化钛光利用效率的有效方法，其吸光范围可从紫外拓展到可见光区域。目前常用的黑色二氧化钛制备方法是通过水热反应得到白色二氧化钛后，将其置于高温氢气氛围中煅烧，诱导其体相中形成钛缺陷或氧空位，以产生黑色二氧化钛。显然，该方法成本较高，不利于大范围的工业应用。
硫化钼作为另一种被广泛研究的光材料，在储能、电子器件及环境修复领域有理想的应用前景。然而，硫化钼的导电性较差，导致光催化过程中产生的光生载流子迁移率受限。
发明内容
为克服以上弊端，本发明提供了一种黑色材料负载金属纳米颗粒的异质结复合催化剂的制备方法，本方法首次提出将二氧化钛前体物与锰盐溶液充分混合后进行溶剂热反应来制备黑色二氧化钛，再通过液相还原法制得金属纳米颗粒/黑色二氧化钛的复合材料。同时，硫化钼纳米花与具有良好导电性的金属纳米颗粒结合制备出金属纳米颗粒/硫化钼纳米花复合催化剂。进一步地，复合催化剂中新型黑色材料与纳米零价金属的钝化层可构建具有强光反应性的异质结，实现抗生素的高效光降解。研究表明，通过液相还原法制备金属纳米颗粒/黑色材料复合催化剂未见报道，同时，将纳米零价金属的钝化层作为半导体与新型黑色材料构建异质结的反应机制也是被首次提出。
本发明黑色材料负载金属纳米颗粒的异质结复合催化剂的制备方法如下：
（1）将1.7~6.8g钛酸丁酯溶于10~50mL异丙醇中并搅拌10min，然后将0.05~0.2452g锰盐用10~50mL去离子水溶解后，并倒入前溶液中，搅拌30min，将形成的均相凝胶倒入反应釜中，在150~250℃下反应4~12h后冷却过夜，用去离子水冲洗并抽滤3次后，在40~80℃下干燥过夜，得到黑色二氧化钛颗粒；
所述锰盐为四水合乙酸锰、二水草酸锰、二水甲酸锰或碳酸锰；
或者，将1.4213~5.6850g四水钼酸铵与2.6262~10.5046g硫脲溶于40~160mL去离子水中并搅拌30min，将形成的均相溶液倒入反应釜中，在120~240℃下反应24h后冷却过夜，用去离子水冲洗并抽滤3次后，在40 ~ 80℃下真空干燥过夜，得到硫化钼纳米花；
（2）将0.25~2g金属盐溶于10~100mL去离子水后，将0.1~4g步骤（1）的黑色二氧化钛颗粒或硫化钼纳米花倒入金属盐溶液中，搅拌20 min后，滴定添加还原剂溶液；
金属盐为铁盐、镍盐、银盐、锌盐、铜盐中的1种或2种，还原剂为硼氢化钾、硼氢化钠、硼氢化钙、硼氢化锌、抗坏血酸或茶多酚，金属盐与还原剂的摩尔比为1:2~1:10；
金属盐为可溶性金属氯化盐、硫酸盐、磷酸盐、碳酸盐或硝酸盐；当金属盐为2种时，两种金属的摩尔比为1:10 ~ 10:1；
（3）滴定完成后继续搅拌30min，依次用去离子水、乙醇和丙酮抽滤清洗材料，真空干燥，得到黑色材料负载金属纳米颗粒的异质结复合催化剂。
本发明另一个目的是将上述方法制得的黑色材料负载金属纳米颗粒的异质结复合催化剂应用在四环素、甲硝唑、环丙沙星、磺胺嘧啶等抗生素废水、重金属废水、染料废水、农药废水的光降解中。
本发明的有益效果如下：
1、二氧化钛前体物与锰盐溶液通过溶剂热反应制备出黑色二氧化钛，无需高温条件和氢气氛围的诱导，制备方法简单，成本显著低廉，操作简单；
2、硫化钼纳米花与金属纳米颗粒结合后，导电性显著提升，光催化性能明显增强；
3、纳米零价金属负载在新型黑色材料上，其分散性被显著改善，可用的反应位点数量增加，吸附和还原性能进一步提升；
4、对抗生素降解活性具有严重抑制作用的纳米零价金属的钝化层被作为半导体与新型黑色材料构建形成异质结，在完全克服纳米零价金属缺点的同时极大地促进抗生素的高效降解；
5、黑色二氧化钛的制备克服了普通二氧化钛的缺点，其吸光范围从紫外光被拓展到可见光区域；
6、纳米零价金属的钝化层被巧妙地作为半导体与新型黑色材料构建异质结，实现高效的抗生素光降解，达到“转危为安”的效果；
7、由于复合材料中纳米零价铁等磁性材料的存在，实现材料的可回收性，避免材料的损失，为工业化提供便利；
8、通过金属纳米颗粒/黑色材料复合催化剂与光催化技术的结合，纳米零价金属的团聚、钝化及二氧化钛可见光利用能力差、硫化钼导电性差等问题被同时解决。
附图说明
图1为本发明通过液相还原法制备得到的纳米零价铁的500nm尺度扫描电镜（SEM）图；
图2为本发明通过液相还原法制备得到的纳米零价铁/黑色二氧化钛复合材料的500nm尺度扫描电镜（SEM）图；
图3为本发明所制备的纳米零价铁/黑色二氧化钛复合材料的EDS分析结果；
图4为纳米零价铁/黑色二氧化钛复合材料暗反应30min后的5nm尺度下的透射电镜（TEM）图；
图5为纳米零价铁钝化层与黑色二氧化钛的紫外可见漫反射（UV-vis DRS）图；
图6为本发明所制备的硫化钼纳米花的500 nm尺度扫描电镜（SEM）图；
图7为本发明通过液相还原法制备得到的纳米零价铁/硫化钼纳米花复合材料的1μm尺度扫描电镜（SEM）图。
具体实施方式
下面通过结合实施例与附图对本发明作进一步详细说明，但本发明保护范围不局限于所述内容。
实施例1：纳米零价铁/黑色二氧化钛的制备及其对四环素的光降解，具体实施内容如下：
（1）3.4g钛酸丁酯溶于25mL异丙醇中并搅拌10min，0.1226g四水合乙酸锰用25mL去离子水溶解，并倒入前溶液中，搅拌30min；所形成的均相凝胶倒入反应釜中，在200℃下反应8h后冷却过夜，用去离子水冲洗并抽滤3次后，在60℃烘箱中干燥过夜得到黑色二氧化钛颗粒；
（2）1g硫酸亚铁溶于20mL去离子水后，1g黑色二氧化钛倒入该溶液中并搅拌20min，硼氢化钾溶液（硫酸亚铁与硼氢化钾的摩尔比为1:5）滴定进入前溶液中；
（3）待滴定完成后搅拌30min，依次用去离子水、乙醇和丙酮清洗材料并抽滤后真空干燥，制得纳米零价铁/黑色二氧化钛复合材料；
同时步骤（2）中不添加黑色二氧化钛制得纳米零价铁，作为对照；
利用300W氙灯（420nm滤波片）考查纳米零价铁、黑色二氧化钛及纳米零价铁/黑色二氧化钛复合材料对四环素的光降解能力，材料的使用量为7mg，30 mg/L四环素溶液的体积为60mL，结果表明，在30min的暗反应及30min的光反应后，纳米零价铁、黑色二氧化钛及复合材料对四环素的降解效率分别为80.51%、35.05%和98.67%。
利用扫描电镜（SEM）分别对纳米零价铁和纳米零价铁/黑色二氧化钛复合材料的形貌结构进行表征，结果如图1、2；从图1可知，所制备的纳米零价铁颗粒间由于其固有磁性而相互吸引，最终呈链状结构；单个颗粒的粒径在100nm左右，呈球形状态但颗粒间的轮廓不明显；显然，链状结构与不明显的颗粒间轮廓不利于纳米零价铁颗粒上可用反应位点的充分暴露，进而严重影响对四环素的降解能力。从图2可知，黑色二氧化钛颗粒粒径很小，其颗粒间相互结合呈现蓬松的类海绵状，其颗粒间丰富的孔道也有利于对四环素的吸附；黑色二氧化钛的存在显著诱导纳米零价铁颗粒间的分散，导致其可用反应位点数量显著增加，进而明显改善对四环素的吸附和还原能力；相对于纯纳米零价铁，复合材料中的纳米零价铁呈规则球形，其轮廓显著且表面光滑；黑色二氧化钛对纳米零价铁的锚定也证明纳米零价铁/黑色二氧化钛复合材料被成功制备。
利用EDS对纳米零价铁/黑色二氧化钛复合材料进行分析。图3的结果证实复合材料中Fe、Ti、Mn、O等元素的存在；结合图3与下表的结果可再次证实纳米零价铁/黑色二氧化钛复合材料的成功制备。
纳米零价铁/黑色二氧化钛复合材料EDS结果所对应的重量百分比与原子百分比数据：
利用透射电镜（TEM）对暗反应30min后的复合材料的结构特征进行表征。由图4的结果表明，复合材料在四环素溶液中暗反应30min后，纳米零价铁的表面产生明显的钝化层。该钝化层可作为光反应阶段的半导体，与黑色二氧化钛构成异质结，实现四环素的高效光降解。
利用紫外可见漫反射（UV-vis DRS）技术对纳米零价铁钝化层与黑色二氧化钛的吸光能力进行评估。如图5所示，纳米零价铁钝化层在200~800nm波长范围内具有优良的吸光性能，反映其对可见光的理想的利用能力。研究表明，二氧化钛的吸收带小于420nm，然而，图中所示的黑色二氧化钛的吸收带从420nm拓展到800nm，表明其吸光范围从紫外光延伸到可见光，有利于四环素的可见光光降解。
以上结果充分表明，纳米零价铁的团聚、钝化与二氧化钛的可见光利用能力差等问题通过纳米零价铁/黑色二氧化钛复合材料与光催化技术的结合被同时解决，同时，该复合材料展现出对四环素等抗生素的理想的光降解性能。
实施例2：纳米零价锌铁双金属/黑色二氧化钛的制备及其对磺胺嘧啶的光降解，具体实施内容如下：
（1）将6.8g钛酸丁酯溶于50mL异丙醇中并搅拌10min，将0.2452g二水草酸锰用50mL去离子水溶解，并倒入前溶液中，搅拌30 min；所形成的均相凝胶倒入反应釜中，在250℃下反应4h后冷却过夜，用去离子水冲洗并抽滤3次后，在80℃烘箱中干燥过夜得到黑色二氧化钛颗粒；
（2）将2g硫酸铁、硫酸锌（锌铁摩尔比为1:5）溶于100mL去离子水后，4g黑色二氧化钛倒入该溶液中并搅拌20min，将硼氢化钙溶液（硫酸铁、硫酸锌与硼氢化钙的摩尔比为1:10）滴定进入前溶液中；
（3）待滴定完成后将该溶液搅拌30min，依次用去离子水、乙醇和丙酮清洗材料并抽滤三次后真空干燥，制备出纳米零价锌铁双金属/黑色二氧化钛复合材料；
同时步骤（2）中不添加黑色二氧化钛制得纳米零价锌铁，作为对照；
利用300 W氙灯（420nm滤波片）考查纳米零价锌铁双金属、黑色二氧化钛及纳米零价锌铁双金属/黑色二氧化钛复合材料对磺胺嘧啶的光降解能力，材料的使用量为12mg，30mg/L磺胺嘧啶溶液的体积为60mL。结果表明，在30min的暗反应及45min的光反应后，纳米零价锌铁双金属、黑色二氧化钛及复合材料对磺胺嘧啶的降解效率分别为58.23%、31.42%和90.53%。
实施例3：纳米零价铁/黑色二氧化钛的制备及其对甲硝唑的光降解，具体实施内容如下：
（1）将1.7g钛酸丁酯溶于10mL异丙醇中并搅拌10min，将0.05g碳酸锰用10mL去离子水溶解，并倒入前溶液中，搅拌3 min；形成的均相凝胶倒入反应釜中，在150℃下反应12h并冷却过夜，用去离子水冲洗并抽滤3次后，在40℃烘箱中干燥过夜得到黑色二氧化钛颗粒；
（2）将0.25g硝酸铁溶于10mL去离子水后，将0.1g黑色二氧化钛倒入硝酸铁溶液中并搅拌20 min，硼氢化钠溶液（硝酸铁与硼氢化钠的摩尔比为1:2）滴定进入前溶液中；
（3）待滴定完成后将该溶液搅拌30min，依次用去离子水、乙醇和丙酮清洗材料并抽滤三次后真空干燥，制备出纳米零价铁/黑色二氧化钛复合材料。
同时步骤（2）中不添加黑色二氧化钛制得纳米零价铁，作为对照；
利用300 W氙灯（420nm滤波片）考查纳米零价铁、黑色二氧化钛及纳米零价铁/黑色二氧化钛复合材料对甲硝唑的光降解能力，材料的使用量为9mg，30 mg/L甲硝唑溶液的体积为60mL。结果表明，在30min的暗反应及60min的光反应后，纳米零价铁、黑色二氧化钛及复合材料对甲硝唑的降解效率分别为42.15%、27.21%和88.52%。
实施例4：纳米零价铜铁双金属/硫化钼纳米花的制备及其对环丙沙星的光降解，具体实施内容如下：
（1）将1.4213 g四水钼酸铵与2.6262g硫脲溶于40mL去离子水中并搅拌30min；形成的均相溶液倒入反应釜中，在120℃下反应24h后冷却过夜，用去离子水冲洗并抽滤3次后，在40℃真空干燥箱中干燥过夜得到硫化钼纳米花；
（2）将1.5g氯化铜、氯化铁（铜铁摩尔比为1:1）溶于80mL去离子水后，将2.5g硫化钼纳米花倒入该溶液中并搅拌20min，将茶多酚溶液（氯化铜、氯化铁与茶多酚的摩尔比为1:8）滴定进入前溶液中；
（3）待滴定完成后将该溶液搅拌30min，依次用去离子水、乙醇和丙酮清洗材料并抽滤三次后真空干燥，制备出纳米零价铜铁双金属/黑色二氧化钛复合材料。
同时步骤（2）中不添加硫化钼纳米花制得纳米零价铜铁，作为对照；
利用300 W氙灯（420 nm滤波片）考查纳米零价铜铁双金属、硫化钼纳米花及纳米零价铜铁双金属/硫化钼纳米花复合材料对环丙沙星的光降解能力，材料的使用量为10mg，30 mg/L环丙沙星溶液的体积为60mL。结果表明，在30min的暗反应及60min的光反应后，纳米零价铜铁双金属、硫化钼纳米花及复合材料对环丙沙星的降解效率分别为45.81%、22.37%和86.46%。
实施例5：纳米零价镍铁双金属/硫化钼纳米花的制备及其对甲硝唑的光降解，具体实施内容如下：
（1）将5.6850 g四水钼酸铵与10.5046 g硫脲溶于160mL去离子水中并搅拌30min；形成的均相溶液倒入反应釜中，在240℃下反应24 h并冷却过夜，用去离子水冲洗并抽滤3次后，在80℃真空干燥箱中干燥过夜得到硫化钼纳米花；
（2）将1.5g磷酸镍、磷酸铁（镍铁摩尔比为1:10）溶于80mL去离子水后，将2g硫化钼纳米花倒入该溶液中并搅拌20min，将抗坏血酸溶液（磷酸镍、磷酸铁与抗坏血酸的摩尔比为1:6）滴定进入前溶液中；
（3）待滴定完成后将该溶液搅拌30min，依次用去离子水、乙醇和丙酮清洗材料并抽滤三次后真空干燥，制备出纳米零价镍铁双金属/硫化钼纳米花复合材料。
同时步骤（2）中不添加硫化钼纳米花制得纳米零价镍铁，作为对照；
利用300 W氙灯（420 nm滤波片）考查纳米零价镍铁双金属、硫化钼纳米花及纳米零价镍铁双金属/硫化钼纳米花复合材料对甲硝唑的光降解能力，材料的使用量为12mg，30mg/L甲硝唑溶液的体积为60mL。结果表明，在30min的暗反应及60min的光反应后，纳米零价镍铁双金属、硫化钼纳米花及复合材料对环丙沙星的降解效率分别为50.34%、32.51%和92.16%。
实施例6：纳米零价铁/硫化钼纳米花的制备及其对四环素的光降解，具体实施内容如下：
（1）将2.8425g四水钼酸铵与5.2523g硫脲溶于80mL去离子水中并搅拌30min；形成的均相溶液倒入反应釜中，在180℃下反应24h并冷却过夜，用去离子水冲洗并抽滤3次后，在60℃真空干燥箱中干燥过夜得到硫化钼纳米花；
（2）将1g硫酸亚铁溶于40mL去离子水后，将1g硫化钼纳米花倒入该溶液中并搅拌20 min，然后将硼氢化钾溶液（硫酸亚铁与硼氢化钾的摩尔比为1:4）滴定进入前溶液中；
（3）待滴定完成后将该溶液搅拌30min，依次用去离子水、乙醇和丙酮清洗材料并抽滤三次后真空干燥，制备出纳米零价铁/硫化钼纳米花复合材料。
同时步骤（2）中不添加硫化钼纳米花制得纳米零价铁，作为对照；
利用300W氙灯（420nm滤波片）考查纳米零价铁、硫化钼纳米花及纳米零价铁/硫化钼纳米花复合材料对四环素的光降解能力，材料的使用量为10mg，30 mg/L四环素溶液的体积为60mL。结果表明，在30min的暗反应及45min的光反应后，纳米零价铁、硫化钼纳米花及复合材料对四环素的降解效率分别为76.54%、30.47%和97.37%。
利用SEM分别对硫化钼纳米花、纳米零价铁/硫化钼纳米花复合材料的形貌结构进行表征，结果如图6、7所示。图6的结果表明，本发明所制备的硫化钼纳米花由大量纳米级薄片状的硫化钼材料结合而成，显然，纳米花结构中丰富的孔道有利于目标污染物的转移与吸附。如图7所示，通过液相还原法所制备的纳米零价铁/硫化钼纳米花复合材料并未破坏硫化钼纳米花的框架。同时，复合材料中的纳米零价铁被限域在纳米花的花瓣中，其固有磁性被克服而呈现出良好的分散性，有利于对抗生素等目标污染物的吸附、还原及光降解。
Claims (7)
1.一种黑色材料负载金属纳米颗粒的复合催化剂的制备方法，其特征在于：利用溶剂热法制备出黑色二氧化钛颗粒或硫化钼纳米花，并利用液相还原法制备得到黑色材料负载金属纳米颗粒的复合催化剂。
2.根据权利要求1所述黑色材料负载金属纳米颗粒的复合催化剂的制备方法，其特征在于，具体步骤如下：
（1）将1.7~6.8g钛酸丁酯溶于10~50mL异丙醇中并搅拌10min，然后将0.05~0.2452g锰盐用10~50mL去离子水溶解后，并倒入前溶液中，搅拌30min，将形成的均相凝胶倒入反应釜中，在150~250℃下反应4~12h后冷却过夜，用去离子水冲洗并抽滤3次后，在40~80℃下干燥过夜，得到黑色二氧化钛颗粒；
或者，将1.4213g~5.6850g四水钼酸铵与2.6262g~10.5046g硫脲溶于40~160mL去离子水中并搅拌30min，将形成的均相溶液倒入反应釜中，在120~240℃下反应24h后冷却过夜，用去离子水冲洗并抽滤3次后，在40 ~ 80℃下真空干燥过夜，得到硫化钼纳米花；
（2）将0.25~2g金属盐溶于10~100mL去离子水后，将0.1~4g步骤（1）的黑色二氧化钛颗粒或硫化钼纳米花倒入金属盐溶液中，搅拌20 min后，滴定添加还原剂溶液；
（3）滴定完成后继续搅拌30min，依次用去离子水、乙醇和丙酮抽滤清洗材料，真空干燥，得到黑色材料负载金属纳米颗粒的复合催化剂。
3.根据权利要求2所述的黑色材料负载金属纳米颗粒的复合催化剂的制备方法，其特征在于：锰盐为四水合乙酸锰、二水草酸锰、二水甲酸锰或碳酸锰。
4.根据权利要求2所述的黑色材料负载金属纳米颗粒的复合催化剂的制备方法，其特征在于：金属盐为铁盐、镍盐、银盐、锌盐、铜盐中的1种或2种，还原剂为硼氢化钾、硼氢化钠、硼氢化钙、硼氢化锌、抗坏血酸或茶多酚，金属盐与还原剂的摩尔比为1:2~1:10。
5.根据权利要求4所述的黑色材料负载金属纳米颗粒的复合催化剂的制备方法，其特征在于：金属盐为可溶性金属氯化盐、硫酸盐、磷酸盐、碳酸盐或硝酸盐。
6.根据权利要求4所述的黑色材料负载金属纳米颗粒的复合催化剂的制备方法，其特征在于：当金属盐为2种时，两种金属的摩尔比为1:10 ~ 10:1。
7.权利要求1-6中任一项所述的黑色材料负载金属纳米颗粒的复合催化剂的制备方法制得的黑色材料负载金属纳米颗粒的复合催化剂在处理抗生素废水、重金属废水、染料废水、农药废水中的应用。
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