CN107088413A - 一种CuO/Cu2O光催化剂及其制备方法与应用 - Google Patents
一种CuO/Cu2O光催化剂及其制备方法与应用 Download PDFInfo
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 42
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 21
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 12
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 11
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- 238000003756 stirring Methods 0.000 claims description 30
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
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- NHMJUOSYSOOPDM-UHFFFAOYSA-N cadmium cyanide Chemical compound [Cd+2].N#[C-].N#[C-] NHMJUOSYSOOPDM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 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
- 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
- B01J23/72—Copper
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- B01J35/39—
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- B01J35/40—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C02—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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- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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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- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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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Abstract
本发明公开了一种CuO/Cu2O光催化剂及其制备方法与应用,其是以铜盐、碱以及抗坏血酸为原料,经沉淀和还原制得所述CuO/Cu2O光催化剂。本发明CuO/Cu2O光催化剂具有较高的催化性能,可用于光催化还原Cr(VI)到Cr(III)或光催化降解水杨酸,从而适用于环境中Cr(VI)的清除和水杨酸的降解。此外,本发明制备成本低,生产工艺简单,可大规模生产,且所得催化剂可以太阳光为驱动能,用于Cr(VI)的还原和水杨酸的降解,有利于环境的可持续发展,具有重要的现实意义。
Description
技术领域
本发明属于环境净化和环境的可持续发展技术领域,具体涉及一种CuO/Cu2O光催化剂及其制备方法与其在光催化还原Cr(VI)和降解水杨酸上的应用。
背景技术
近几十年来,现代工业、农业和交通运输业给人类社会带来物质文明的同时也给生态环境和人类带来了极大的破坏和伤害,人们受到重金属的危害呈现频发和加剧状态。重金属主要来源于生活和工业污染,生活中重金属主要来源有油漆、涂料,釉彩碗碟、餐具、燃煤,物品中报纸油墨、化妆品、染发剂、餐具、玩具、皮革橡胶、油漆涂料、废旧电池、各种杀虫剂、杀鼠剂、化肥农药等;工业上重金属主要来源有电镀、电路板、燃料、皮革、颜料、劣质化妆品原料、化学制药废液、脱色剂、砷酸盐药物、塑料稳定剂、燃料燃烧等。在交通运输业中重金属来源于汽车尾气以及汽车轮胎磨损产生的大量含重金属的粉尘和气体。
重金属在人体内能和蛋白质及酶等发生强烈的相互作用,使它们失去活性,也可能在人体的某些器官中累积,造成慢性中毒。重金属离子进入到土壤达到较高浓度时,将导致微生物的含量降低,进而影响土壤微生物的多样性,而植物吸入重金属离子同样会降低酶的活性而影响代谢作用,对于可食用的植物将最终通过食物链进入到人的体内,在人体中累积;同时,重金属离子进入到水体中,会被水生动植物吸收富集,亦可通过饮用水或是食用水体动物进入人体内;重金属离子进入到空气中,直接通过呼吸作用进入到人体内。同时,重金属污染与其他有机化合物的污染不同。不少有机化合物可以通过自然界本身物理的、化学的或生物的净化,使有害性降低或解除,而重金属具有富集性,很难在环境中降解。总而言之,重金属离子产生的危害终会直接或间接影响到人们的身心健康。
目前,除去水中重金属离子的方法有很多,主要有:氧化还原法、电化学法、中和法、化学沉淀法、膜分离法、活性污泥法、植物提取修复技术、生物膜法等。其中处理Cr(VI)常用的方法有铁氧体法(使废水中的铬离子形成铁氧体晶粒一起沉淀析出)、化学还原法(添加还原剂使水中的铬离子还原析出)、活性炭吸附法;处理铅的常用方法有化学沉淀法(含铅离子的废水中加入沉淀剂或无机絮凝剂使其沉淀分离除去)、离子树脂交换法、腐植酸煤吸附法;处理镉常用的方式是加碱处理无氰镀镉废水,加漂白粉或次氯酸钠处理氰化镀镉废水,或者应用腐植酸树脂处理镀镉钝化漂洗水、氰化镀镉漂洗水、无氰镀镉漂洗水。处理土壤中重金属的方法有化学稳定法(通过添加稳定剂,使重金属向难溶态转变,从而达到消除的目的)、化学还原法(向土壤中施用还原剂,将可变价金属还原成低价态,从而易被粘土颗粒吸附)。对于大气中的污染物主要是靠植物吸收,在道路两旁划出绿化带。而采用光催化技术进行处理,不仅绿色环保,而且处理效果好,将其用于重金属等污染物的降解处理具有良好发展前景。
发明内容
本发明的目的在于提供一种CuO/Cu2O光催化剂及其制备方法与应用,其所得催化剂催化效率高、使用寿命长、对环境友好,可用于光催化还原Cr(VI)和光催化降解水杨酸,且其制备成本低、生产工艺简单、可大规模生产。
为实现上述目的,本发明采用如下技术方案:
一种CuO/Cu2O光催化剂呈正方体形状,由小颗粒和小片状构成,其尺寸为0.3~0.4 μm×0.3~0.4 μm。
所述CuO/Cu2O光催化剂的制备方法包括以下步骤:
1)将CuSO4·5H2O溶解于去离子水中,形成硫酸铜溶液;
2)在步骤1)所得硫酸铜溶液中,边搅拌边缓慢滴加NaOH溶液,滴加完后继续搅拌30min,以形成悬浮液;
3)在步骤2)所得悬浮液中边搅拌边缓慢滴加抗坏血酸溶液,然后继续搅拌30 min,生成大量固体;
4)将步骤3)所得固体过滤分离,用乙醇洗涤后,再用去离子水洗涤至pH为7,干燥得所述CuO/Cu2O光催化剂。
其中,所用CuSO4·5H2O与NaOH、抗坏血酸的摩尔比为1:6:0.22~0.27。
本发明所得CuO/Cu2O光催化剂可用于光催化还原Cr(VI)到Cr(III),或用于光催化降解水杨酸。
本发明的显著优点在于:
(1)本发明CuO/Cu2O光催化剂呈正方体形状,由小颗粒和小片状构成,在光催化过程中能提供更多的活性位点,从而有利于提高光催化效率,并可拓展所得光催化剂在光催化氧化和还原方面的应用;且其制备成本低,生产工艺简单,可大规模生产。
(2)本发明CuO/Cu2O光催化剂可用于光催化还原Cr(VI)及降解水杨酸,并具有高催化效率,在Cr(VI)的还原试验中,其反应80 min的还原率为99.2%;在水杨酸的降解试验中,其反应120 min的降解率为89.3 %。
(3)本发明所得CuO/Cu2O光催化剂可通过离心回收循环使用,其回收率可达99.2%,有利于环境和能源的可持续发展,且经检测证实,其经8次重复光催化反应后催化活性仍能保持稳定。
附图说明
图1为经不同量抗坏血酸还原得到的CuO、Cu(OH)2/Cu2O、CuO/Cu2O和Cu2O的X射线衍射图。
图2为经不同量抗坏血酸还原得到的CuO(a)、Cu(OH)2/Cu2O(b)、CuO/Cu2O(c)和Cu2O(d)的扫描电镜图。
图3为经不同量抗坏血酸还原得到的CuO、Cu(OH)2/Cu2O、CuO/Cu2O和Cu2O的紫外-可见漫反射图。
图4为CuO/Cu2O光催化还原Cr(VI)(a)和光催化降解水杨酸(b)的循环实验图。
具体实施方式
一种CuO/Cu2O光催化剂的制备方法包括以下步骤:
1)将2.497 g(10 mmol)CuSO4·5H2O溶解于100 mL去离子水中,形成浓度为0.1mol/L的硫酸铜溶液;
2)在步骤1)所得硫酸铜溶液中边搅拌边缓慢滴加40 mL、1.5 mol/L的NaOH溶液,滴加完后继续搅拌30 min,以形成悬浮液;
3)在步骤2)所得悬浮液中边搅拌边缓慢滴加22 mL~27 mL 0.1 mol/L抗坏血酸溶液,然后继续搅拌30 min,生成大量固体;
4)将步骤3)所得固体过滤分离,用乙醇洗涤后,再用去离子水洗涤至pH为7,干燥得CuO/Cu2O光催化剂。
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 CuO/Cu2O的制备
将2.497 g(10 mmol)CuSO4·5H2O溶解于100 mL去离子水中,形成0.1mol/L的硫酸铜溶液;将所得溶液边搅拌边缓慢滴加40 mL、1.5 mol/L的NaOH溶液,继续搅拌30 min,形成悬浮液;在所得悬浮液中边搅拌边缓慢滴加25 mL、0.1 mol/L抗坏血酸溶液,继续搅拌30min;所得固体过滤分离,用乙醇洗涤,再用去离子水洗涤至pH为7,干燥得CuO/Cu2O光催化剂。
对比例1 CuO的制备
将2.497 g(10 mmol)CuSO4·5H2O溶解于100 mL去离子水中,形成0.1mol/L的硫酸铜溶液;将所得溶液边搅拌边缓慢滴加40 mL、1.5 mol/L的NaOH溶液,继续搅拌30 min,形成悬浮液;然后将所得固体过滤分离,用乙醇洗涤,再用去离子水洗涤至pH为7,干燥得CuO光催化剂。
对比例2 Cu(OH)2/Cu2O的制备
将2.497 g(10 mmol)CuSO4·5H2O溶解于100 mL去离子水中,形成0.1mol/L的硫酸铜溶液;将所得溶液边搅拌边缓慢滴加40 mL、1.5 mol/L的NaOH溶液,继续搅拌30 min,形成悬浮液;将所得悬浮液边搅拌边缓慢滴加10 mL、0.1 mol/L抗坏血酸溶液,继续搅拌30min;所得固体过滤分离,用乙醇洗涤,再用去离子水洗涤至pH为7,干燥得Cu(OH)2/Cu2O光催化剂。
对比例3 Cu2O的制备
将2.497 g(10 mmol)CuSO4·5H2O溶解于100 mL去离子水中,形成0.1mol/L的硫酸铜溶液;将所得溶液边搅拌边缓慢滴加40 mL、1.5 mol/L的NaOH溶液,继续搅拌30 min,形成悬浮液;将所得悬浮液边搅拌边缓慢滴加30 mL、0.1 mol/L抗坏血酸溶液,继续搅拌30min;所得固体过滤分离,用乙醇洗涤,再用去离子水洗涤至pH为7,干燥得Cu2O光催化剂。
图1是加入不同量抗坏血酸还原得到的铜基光催化剂的X射线衍射谱图。由图中可以看出,未加入抗坏血酸制得的样品有两个比较强的衍射峰,其位置在35.5°和38.7°,对应于(-111)和(111)晶面,即所得样品为CuO(JCPDS No. 80-1916)。加入10 mL抗坏血酸时制得的样品的衍射峰在16.7°、23.8°、34.1°、35.9°、39.8°和53.4°对应于(020)、(021)、(002)、(111)、(130)和(132)晶面,即Cu(OH)2(JCPDS No. 80-0656);此外,四个衍射峰在36.4°、42.3°、61.3°和73.5°对应于(111)、(200)、(220)和(311)晶面,可归属为Cu2O(JCPDSNo. 05-0667),此时所得样品为Cu(OH)2/Cu2O。加入25 mL抗坏血酸时制得的样品出现35.5°和38.7°衍射峰,以及36.4°、42.3°、61.3°和73.5°衍射峰,即所得样品为CuO/Cu2O。加入30mL抗坏血酸制得的样品只能观测到明显的衍射峰在36.4°、42.3°、61.3°和73.5°位置,即所得样品为Cu2O。
图2是加入不同量抗坏血酸还原得到的铜基光催化剂的扫描电镜图。由图中可以看出,未加入抗坏血酸制得的样品呈片状,片上具褶皱;加入10 mL抗坏血酸时制得的样品呈棒状,由片状物质破碎所得;加入25 mL抗坏血酸制得的样品呈正方体形状,由小颗粒和小片状构成,尺寸为0.3~0.4 μm×0.3~0.4 μm;加入30 mL抗坏血酸制得的样品呈球形,由小颗粒组成。
图3是加入不同量抗坏血酸还原得到铜基光催化剂的紫外-可见漫反射图。从谱图中可以看出,四个样品的固体紫外-可见漫反射趋势类似,在紫外到可见区都具有比较好的吸收。
1. Cr(VI)光催化还原试验
在150 mL光催化反应器中,加入0.1 g光催化剂和80 mL、10 mg/L的Cr(VI)溶液,搅拌混合均匀;然后将混合溶液置于光催化反应体系中,先在暗环境下搅拌使其达到吸附-脱附平衡,然后取样,标记此时Cr(VI)溶液的浓度为C 0 ;开灯(光源为氙灯,光源波长为320~780nm)并计时,在线取样,离心回收催化剂后,通过紫外-可见分光光度计测定溶液中剩余Cr(VI)的浓度C;以紫外-可见吸收光谱中369 nm处的变化计算得到Cr(VI)的还原率,所得数据见表1。
表1 光催化还原Cr(VI)的活性数据
由表1结果可见,CuO/Cu2O对Cr(VI)的还原率明显高于CuO、Cu(OH)2/Cu2O和Cu2O。
2.水杨酸光催化降解试验
在150 mL光催化反应器中,加入0.1 g光催化剂和80 mL、25 mg/L的水杨酸,搅拌混合均匀;然后将混合溶液置于光催化反应体系中,先在暗环境下搅拌使其达到吸附-脱附平衡,然后取样,标记此时水杨酸溶液的浓度为C 0 ;开灯(光源为氙灯,光源波长为320~780nm)并计时,在线取样,离心回收催化剂后,通过紫外-可见分光光度计测定溶液中剩余水杨酸的浓度C;以紫外-可见吸收光谱中296 nm处的变化计算得到水杨酸的降解率,所得数据见表2。
表2 光催化降解水杨酸的活性数据
由表2结果可见,CuO/Cu2O对水杨酸的降解率明显高于CuO、Cu(OH)2/Cu2O和Cu2O。
由上述实验证明,本发明所得CuO/Cu2O可用于光催化还原Cr(VI)和降解水杨酸,并具有高催化效率。
图4为CuO/Cu2O光催化还原Cr(VI)(a)和光催化降解水杨酸(b)的循环实验图。从图中可以看出,经8次重复光催化反应,其仍有较好的Cr(VI)还原率和对水杨酸的降解率,证明其催化活性稳定。
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 (4)
1. 一种CuO/Cu2O光催化剂,其特征在于:所述光催化剂呈正方体形状,由小颗粒和小片状构成,其尺寸为0.3~0.4 μm×0.3~0.4 μm。
2.一种如权利要求1所述CuO/Cu2O光催化剂的制备方法,其特征在于:包括以下步骤:
1)将CuSO4·5H2O溶解于去离子水中,形成硫酸铜溶液;
2)在步骤1)所得硫酸铜溶液中,边搅拌边缓慢滴加NaOH溶液,滴加完后继续搅拌30min,以形成悬浮液;
3)在步骤2)所得悬浮液中边搅拌边缓慢滴加抗坏血酸溶液,然后继续搅拌30 min,生成大量固体;
4)将步骤3)所得固体过滤分离,用乙醇洗涤后,再用去离子水洗涤至pH为7,干燥得所述CuO/Cu2O光催化剂。
3.根据权利要求2所述CuO/Cu2O光催化剂的制备方法,其特征在于:所用CuSO4·5H2O与NaOH、抗坏血酸的摩尔比为1:6:0.22~0.27。
4.一种如权利要求1所述CuO/Cu2O光催化剂的应用,其特征在于:用于光催化还原Cr(VI)到Cr(III),或用于光催化降解水杨酸。
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