CN108404926A - 一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂及其制备方法和应用 - Google Patents
一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于纳米复合材料技术领域,具体公开了一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂及其制备方法和应用。所述制备方法步骤如下:将硝酸铋的丙三醇溶液、石墨烯粉末、偏钒酸铵水溶液和硝酸铁溶液混合得到前驱体溶液,进行水热反应,加入抗坏血酸溶液并在惰性气体保护下静置,用无水乙醇和去离子水交替洗涤,经干燥后即得到无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂。采用上述方法制备得到的无定形钒酸铁/钒酸铋/石墨烯复合光催化剂粒径小于50nm,具有较大的比表面积,其光催化活性也远远超过纯钒酸铋或钒酸铁,可用于光催化还原Cr(VI)及含铬废水的深度处理中,具有广阔的应用前景。
Description
技术领域
本发明涉及纳米复合材料技术领域,具体地,涉及一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂及其制备方法和应用。
背景技术
随着全球经济的迅猛发展,环境污染问题日益突出,重金属污染尤为严重。其中,含铬(通常是Cr(VI))有机废水污染主要来源于工业颜料废水、皮革制剂废水、电镀废水等,此类废水可生化程度低,处理难度大,而目前高级氧化技术所用到的催化剂,往往只能单一地处理有机污染物,而不兼具处理六价铬等重金属的能力。传统技术研究中,以二氧化钛为核心代表的半导体光催化技术被广泛应用于环境污染治理领域,但二氧化钛的带隙宽度为3.2eV,仅在紫外光照射下有反应,实用性较差。因此,为治理含铬有机废水的污染问题,现亟待开发一种能在可见光下有效降解Cr(VI)的新型光催化剂。
钒酸铋作为一种具备可见光响应活性的半导体,主要存在三种晶型:四方锆石型(zt),四方白钨矿型(s-t),单斜白钨矿型(s-m)。其中,单斜相钒酸铋的禁带宽度约为2.40eV,可见光照下即可产生光生电子和光生空穴,在水溶液中具有优异的化学稳定性,无毒害且制备成本低。钒酸铋在降解有机污染物、光解水制氢制氧等技术领域具有广阔的发展前景。但纯相钒酸铋本身仍存在光生载流子易复合、表面吸附能力差的缺点。
石墨烯中的碳原子以六元环形式排列于单原子层平面内,具有四个价电子的C原子贡献一个未成键的价电子。这些价电子在单原子层的二维晶体结构中与平面垂直的方向形成共轭的离域大键,因此电子可在晶体中自由移动,使石墨烯具有优异的电子传导性能。此外,石墨烯还具有优异的机械性能及对光的高透过性以及高比表面积,可用来制备石墨烯各种功能化复合材料。石墨烯突出的性能及其易加工性使其在光催化领域具有很好的应用前景,其优异的导电性能,可将光生电子更快地传导到材料表面,有效分离了光生电子-空穴对,降低了它们的复合率。
已有研究已证实,在钒酸铋表面负载少量石墨烯一定程度上可促进钒酸铋晶体{010}晶面的优先生长,该晶面的优先生长有助于提高光生电子空穴对的分离效率。同时,石墨烯表面存在大量源自sp2连结的共轭碳网络去局域化电子,因而具有良好的导电性,能进一步加快光生载流子在钒酸铋复合材料表面的传导。但是,目前已报道的钒酸铋-石墨烯复合材料多为规则的晶态结构,粒径大小也多在100~200nm之间,比表面积较小,其光催化性能仍有待提高;而至于非晶态的无定形复合材料则普遍存在晶粒尺寸较大,吸附能力差,光生载流子难以分离,电子空穴对容易复合使得光催化效率较低的缺陷。
发明内容
本发明的目的是为了克服现有技术的上述不足,提供一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂的制备方法,通过该方法制备得到的复合光催化剂粒径小于50nm,具有较高的比表面积,其光催化活性也远远超过纯钒酸铋或钒酸铁。
本发明的另一目的在于提供一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂。
本发明的另一目的在于提供上述无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂在光催化还原Cr(VI)和/或含铬废水的深度处理中的应用。
为了实现上述目的,本发明是通过以下方案予以实现的:
一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂的制备方法,包括如下步骤:
S1.配制硝酸铋的丙三醇溶液,加入石墨烯粉末,超声、搅拌10~15min;
S2.配制偏钒酸铵水溶液和硝酸铁溶液;将S1中处理后的硝酸铋的丙三醇溶液和硝酸铁溶液混匀,澄清后加入偏钒酸铵水溶液,搅拌15~30min,调节pH值至4~7,得到前驱体溶液,静置、老化1~2h;
S3.将S2所得前驱体溶液置于158~162℃条件下恒温进行水热反应10~20h,得到亮黄色悬浊液;
S4.将S3所得亮黄色悬浊液静置10~30min,弃去1/2体积上清液后,加入抗坏血酸溶液,在惰性气体保护下静置0.5~1h;用无水乙醇和去离子水交替洗涤3次,于60℃干燥10~20h,即得到无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂。
由于非晶态的无定形复合材料存在光生载流子难以分离的问题,而改善光生载流子分离效率的方法包括贵金属沉积、与其他半导体复合形成异质结等。本发明选择在制备过程中添加适宜比例的钒酸铁,钒酸铁的能带隙为2.05eV,钒酸铁价带和导带位置与钒酸铋相匹配,两者之间可形成异质结。
更具体的原理如下:钒酸铋能带中包含由Bi 6s和O 2p组成的杂化轨道和V 3d轨道组成的导带,因而能带隙减小,对光的吸收延伸至可见光区。钒酸铁则具有更窄的能带隙,所吸收的光谱波段延伸至更大的可见光区。含有钒酸铋和钒酸铁的前驱体溶液在有丙三醇的环境下进行水热反应产生的无定形样品,与纯的钒酸铋或钒酸铁相比,一是因无定形的钒酸铋/钒酸铁异质结的界面效应(主要是界面间内建电场加速光生电子-空穴对的分离)形成,两者接触界面处能带隙降至1.85eV,光吸收区进一步扩展到近红外区,对500~800nm范围内的光有较强吸收,光生电子-空穴对大量迁移至复合光催化剂材料表面,提高光生电子和光生空穴与污染物接触几率,从而提高复合材料的光催化活性;二是无定形状态样品纳米颗粒尺寸比结晶态样品小一个数量级左右,因而其比表面积相比结晶态的钒酸铋或钒酸铁更大,具有更多的活性位点,能更多的接触水体中的污染物。其中,复合光催化剂材料表面吸附的Cr2O7 2-作为光生电子受体,被还原为低毒的Cr(III),进一步促进了光生电子空穴对的分离,促使光生空穴更多地接触到吸附于材料表面的小分子有机物,将其氧化降解。
因此,本发明以石墨烯为导电薄膜和生长模板,将硝酸铁溶液、硝酸铋的丙三醇溶液与偏钒酸铵水溶液按照一定的摩尔比混合,通过常规水热反应,制备得到粒径小于50nm的无定形钒酸铁/钒酸铋/石墨烯复合光催化剂,既利用了钒酸铋/钒酸铁异质结结构(p-n异质结)和石墨烯导电层来促进光生载流子的分离和传导,使得在可见光照射下激发产生的光生电子-空穴对的分离率大大提高;也利用非晶、无定形结构特有的较大比表面积,从而增加复合光催化剂本身与水体中Cr(VI)接触面,使复合光催化剂比一般的结晶材料拥有更多的光催化活性位点,极大地提高了复合光催化材料的光催化性能。
优选地,所述硝酸铋的丙三醇溶液中,硝酸铋的浓度为30~60mmol/L;所述偏钒酸铵水溶液的浓度为60~100mmol/L;所述硝酸铁溶液的浓度为30~60mmol/L;所述抗坏血酸溶液的浓度为0.2mol/L。
更优选地,所述硝酸铋的丙三醇溶液中,硝酸铋的浓度为40mmol/L;所述偏钒酸铵水溶液的浓度为80mmol/L;所述硝酸铁溶液的浓度为40mmol/L。
优选地,所述硝酸铋的丙三醇溶液、偏钒酸铵水溶液、硝酸铁溶液、抗坏血酸溶液的体积比依次为5~20:10~20:4~8:2~5。更优选地,所述硝酸铋的丙三醇溶液、偏钒酸铵水溶液、硝酸铁溶液、抗坏血酸溶液的体积分别为50~200mL、100~200mL、40~80mL、20~50mL。
优选地,S1中所述硝酸铋与石墨烯粉末的质量比为1.94:0.004~0.032。
优选地,S2中所述配制偏钒酸铵水溶液的温度为60~90℃。更优选地,S2中所述配制偏钒酸铵水溶液的温度为70~80℃。
优选地,S2中所述调节pH值的具体步骤为用氨水调节pH值至6。
优选地,S3中所述水热反应在具有Teflon内衬的不锈钢高压釜中进行。
优选地,S3中所述水热反应时间为12h。
所述的硝酸铋为Bi(NO3)3•5H2O,硝酸铁为Fe(NO3)3•9H2O,钒酸铋为BiVO4,钒酸铁为FeVO4。
本发明还请求保护一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂,由上述方法制备得到,其粒径小于50nm;其中,钒酸铋与钒酸铁的摩尔比为1~4:1,石墨烯的质量百分数为0.5~2.4%。
所述复合光催化剂紫外和可见光区均有较强的吸收,复合光催化剂中钒酸铋与钒酸铁的摩尔比为1:1、2:1、3:1、4:1的能带隙分别为2.23eV、1.98eV、2.09eV、2.06eV,均小于钒酸铋的能带隙(2.40eV);其中,钒酸铋与钒酸铁摩尔比为2:1的复合光催化剂带隙能最小,小于纯钒酸铁的能带隙(2.05eV),因此制备得到的复合光催化剂具有良好的可见光响应性能。
本发明所提供的无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂在光催化含六价铬的复合污染物的实验中,钒酸铋:钒酸铁摩尔比为1:1的复合材料样品的光催化还原六价铬效果最好,180min内对Cr(VI)的去除率达到90%。
因此,本发明还请求保护上述无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂在光催化还原Cr(VI)和/或含铬废水的深度处理中的应用。
与现有技术相比,本发明具有以下有益效果:
本发明的无定形钒酸铁/钒酸铋/石墨烯复合光催化剂,既利用了钒酸铋/钒酸铁异质结结构(p-n异质结)和石墨烯导电层来促进光生载流子的分离和传导,使得在可见光照射下激发产生的光生电子-空穴对的分离率大大提高;也利用非晶、无定形结构特有的较大比表面积,从而增加复合光催化剂本身与水体中Cr(VI)接触面,使复合光催化剂比一般的结晶材料拥有更多的光催化活性位点,极大地提高了复合光催化材料的光催化性能,可用于光催化还原Cr(VI)及含铬废水的深度处理中,具有广阔的应用前景。
附图说明
图1为本发明制备的钒酸铁/钒酸铋/石墨烯复合光催化剂的成品图。
图2为本发明制备的钒酸铁/钒酸铋/石墨烯复合光催化剂的XRD衍射图;其中,a为实施例1所得复合光催化剂,b为实施例2所得复合光催化剂,c为实施例3所得复合光催化剂。
图3为本发明制备的钒酸铁/钒酸铋/石墨烯复合光催化剂的TEM电镜图。
图4为本发明制备的钒酸铁/钒酸铋/石墨烯复合光催化剂的UV-vis 吸收光谱;其中,a为实施例1所得复合光催化剂,b为实施例2所得复合光催化剂,c为实施例3所得复合光催化剂。
图5为本发明制备的钒酸铁/钒酸铋/石墨烯复合光催化剂在可见光下对Cr(VI)的还原曲线;其中,a为实施例1所得复合光催化剂,b为实施例2所得复合光催化剂,c为实施例3所得复合光催化剂。
具体实施方式
下面结合说明书附图及具体实施例对本发明作出进一步地详细阐述,所述实施例只用于解释本发明,并非用于限定本发明的范围。下述实施例中所使用的试验方法如无特殊说明,均为常规方法;所使用的材料、试剂等,如无特殊说明,为可从商业途径得到的试剂和材料。
实施例1
一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂的制备方法,包括如下步骤:
1、准确称取1.94g Bi(NO3)3•5H2O,加到80mL丙三醇中,超声、分散10min,加入0.032g石墨烯粉末,继续超声、搅拌10min;
2、准确称取0.94g NH4VO3,加到100mL去离子水中,在80℃下水浴加热、搅拌直至白色粉末完全溶解;
3、准确称取1.62g Fe(NO3)3•9H2O,溶解于50mL去离子水,将其加到步骤1所得硝酸铋的丙三醇溶液中,搅拌使其均匀澄清后,在磁力搅拌下,逐滴加入步骤2所得偏钒酸铵水溶液,然后继续搅拌20min,用氨水调节pH值至6,得到前驱体溶液,在室温下静置、老化1h;
4、将步骤3所得前驱体溶液转移到具有Telflon内衬的不锈钢高压釜中,在160℃下恒温进行水热反应12h,得到亮黄色悬浊液;
5、将步骤4所得亮黄色悬浊液静置20min,弃去1/2体积上清液后,加入40mL 0.2mol/L抗坏血酸溶液,在惰性气体的保护下,静置1h;用无水乙醇和去离子水交替洗涤3次,于60℃烘箱中干燥10h,即得到无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂粉末。所得到的复合光催化剂中石墨烯的质量百分数为1.6wt%(理论计算),钒酸铁:钒酸铋摩尔比为1:1。
实施例2
一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂的制备方法,包括如下步骤:
1、准确称取1.94g Bi(NO3)3•5H2O,加到80mL丙三醇中,超声、分散10min,加入0.016g石墨烯粉末,继续超声、搅拌10min;
2、准确称取0.94g NH4VO3,加到100mL去离子水中,在80℃下水浴加热、搅拌直至白色粉末完全溶解;
3、准确称取1.62g Fe(NO3)3•9H2O,溶解于50mL去离子水,将其加到步骤1所得硝酸铋的丙三醇溶液中,搅拌使其均匀澄清后,在磁力搅拌下,逐滴加入步骤2所得偏钒酸铵水溶液,然后继续搅拌20min,用氨水调节pH值至6,得到前驱体溶液,在室温下静置、老化1h;
4、将步骤3所得前驱体溶液转移到具有Telflon内衬的不锈钢高压釜中,在160℃下恒温进行水热反应12h,得到亮黄色悬浊液;
5、将步骤4所得亮黄色悬浊液静置20min,弃去1/2体积上清液后,加入40mL 0.2mol/L抗坏血酸溶液,在惰性气体的保护下,静置1h;用无水乙醇和去离子水交替洗涤3次,于60℃烘箱中干燥10h,即得到无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂粉末。所得到的复合光催化剂中石墨烯的质量百分数为0.8wt%(理论计算),钒酸铁:钒酸铋摩尔比为1:1。
实施例3
一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂的制备方法,包括如下步骤:
1、准确称取1.94g Bi(NO3)3•5H2O,加到80mL丙三醇中,超声、分散10min,加入0.032g石墨烯粉末,继续超声、搅拌10min;
2、准确称取1.4g NH4VO3,加到100mL去离子水中,在80℃下水浴加热、搅拌直至白色粉末完全溶解;
3、准确称取1.62g Fe(NO3)3•9H2O,溶解于50mL去离子水,将其加到步骤1所得硝酸铋的丙三醇溶液中,搅拌使其均匀澄清后,在磁力搅拌下,逐滴加入步骤2所得偏钒酸铵水溶液,然后继续搅拌20min,用氨水调节pH值至6,得到前驱体溶液,在室温下静置、老化1h;
4、将步骤3所得前驱体溶液转移到具有Telflon内衬的不锈钢高压釜中,在160℃下恒温进行水热反应12h,得到亮黄色悬浊液;
5、将步骤4所得亮黄色悬浊液静置20min,弃去1/2体积上清液后,加入40mL 0.2mol/L抗坏血酸溶液,在惰性气体的保护下,静置1h;用无水乙醇和去离子水交替洗涤3次,于60℃烘箱中干燥10h,即得到无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂粉末。所得到的复合光催化剂中石墨烯的质量百分数为0.96wt%(理论计算),钒酸铁:钒酸铋摩尔比为1:2。
实施例1~3所得最终产品的外观如图1所示,所制备的复合光催化剂的呈现暗绿色,质地蓬松易磨碎。
实施例1~3所得复合光催化剂的X射线衍射图(XRD)如图2所示,显示在2 Theta=25~30°处均有一个“馒头峰”,均未显示任何FeVO4和BiVO4有关的特征峰,表明样品呈非晶、无定形态。
所述复合光催化剂的透射电镜图(TEM)如图3所示,从图中可清晰看出,粒径<50nm的细小球形纳米颗粒被石墨烯包裹,而在光催化反应中,石墨烯能极好地传导光生电子。
所述的复合光催化剂的固体紫外-可见漫反射(UV-vis)吸收光谱如图4所示,据此估算,对应于实施例1~3所述的复合光催化剂的能带隙分别为2.27eV、2.14eV、2.12eV,表明所制备的复合光催化剂具有良好的可见光响应性能。
应用例
分别取0.1g实施例1~3所制得的无定形钒酸铁/钒酸铋/石墨烯复合光催化剂,加到250mL含5mg/L K2Cr2O7和体积含量为0.2%的甲醇的混合溶液中,进行磁力搅拌,以低瓦数(30W)白光LED为可见光源,进行时长为180min的光催化反应。
实施例1~3所制得的复合光催化剂对Cr(VI)的还原效果如图5所示:从中可看出,实施例1所制备的复合光催化剂在180min内对Cr(VI)去除率达到90%以上,具有的较高的量子效率。溶液中低浓度的甲醇作为光生空穴的牺牲剂,抑制了催化剂表面的光生电子与光生空穴复合,与材料内部的异质结共同作用下,促进光生电子-空穴对的分离,高毒性的Cr(VI)被吸附到复合光催化剂表面,作为光生电子受体而被还原为低毒的Cr(III)。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,对于本领域的普通技术人员来说,在上述说明及思路的基础上还可以做出其它不同形式的变化或变动,这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (10)
1.一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂的制备方法,其特征在于,包括如下步骤:
S1.配制硝酸铋的丙三醇溶液,加入石墨烯粉末,超声、搅拌10~15min;
S2.配制偏钒酸铵水溶液和硝酸铁溶液;将S1中处理后的硝酸铋的丙三醇溶液和硝酸铁溶液混匀,澄清后加入偏钒酸铵水溶液,搅拌15~30min,调节pH值至4~7,得到前驱体溶液,静置、老化1~2h;
S3.将S2所得前驱体溶液置于158~162℃条件下恒温进行水热反应10~20h,得到亮黄色悬浊液;
S4.将S3所得亮黄色悬浊液静置10~30min,弃去1/2体积上清液后,加入抗坏血酸溶液,在惰性气体保护下静置0.5~1h;用无水乙醇和去离子水交替洗涤3次,于60℃干燥10~20h,即得到无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂。
2.根据权利要求1所述的制备方法,其特征在于,所述硝酸铋的丙三醇溶液中,硝酸铋的浓度为30~60mmol/L;所述偏钒酸铵水溶液的浓度为60~100mmol/L;所述硝酸铁溶液的浓度为30~60mmol/L;所述抗坏血酸溶液的浓度为0.2mol/L。
3.根据权利要求2所述的制备方法,其特征在于,所述硝酸铋的丙三醇溶液、偏钒酸铵水溶液、硝酸铁溶液、抗坏血酸溶液的体积比依次为5~20:10~20:4~8:2~5。
4.根据权利要求1所述的制备方法,其特征在于,S1中所述硝酸铋与石墨烯粉末的质量比为1.94:0.004~0.032。
5.根据权利要求1所述的制备方法,其特征在于,S2中所述配制偏钒酸铵水溶液的温度为60~90℃。
6.根据权利要求5所述的制备方法,其特征在于,S2中所述配制偏钒酸铵水溶液的温度为70~80℃。
7.根据权利要求1所述的制备方法,其特征在于,S2中所述调节pH值的具体步骤为用氨水调节pH值至6。
8.根据权利要求1所述的制备方法,其特征在于,所述的硝酸铋为Bi(NO3)3•5H2O,硝酸铁为Fe(NO3)3•9H2O。
9.一种无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂,其特征在于,由权利要求1至8任一项所述制备方法制备得到,其粒径小于50nm;其中,钒酸铋与钒酸铁的摩尔比为1~4:1,石墨烯的质量百分数为0.5~2.4%。
10.权利要求9所述无定形的钒酸铁/钒酸铋/石墨烯复合光催化剂在光催化还原Cr(VI)和/或含铬废水的深度处理中的应用。
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