CN110860313A - 一种纳米氧化锌/铁酸锌/木粉三元复合材料及其制备方法和应用 - Google Patents
一种纳米氧化锌/铁酸锌/木粉三元复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种纳米氧化锌/铁酸锌/木粉三元复合材料及其制备方法和应用,属于纳米复合材料技术领域。该制备方法利用桑枝木粉制备ZnO基三元复合材料,采用低温NaOH/尿素溶液将桑枝木粉部分溶解,加入纳米铁酸锌和锌源,通过水热法原位复合制备纳米氧化锌/铁酸锌/桑枝木粉复合材料。本发明制备方法简单,溶剂NaOH/尿素价廉易得,桑枝木粉属于农林废弃物,实现废弃物资源化利用;制备的氧化锌/铁酸锌/木粉三元复合材料在紫外和可见光区都有吸收,且稳定,环保易回收。在作为光降解催化剂处理亚甲基蓝废水的处理方面,具有很好的实用性。
Description
技术领域
本发明属于纳米复合材料技术领域,具体涉及一种纳米氧化锌/铁酸锌/木粉三元复合材料及其制备方法和应用。
背景技术
随着世界各国经济的迅速发展,环境污染和能源短缺问题日益严重,水体中的有机污染物对人类健康和生态系统造成了严重威胁。半导体光催化剂能够通过氧化还原反应分解有机污染物,在降解处理污水有机物方面有良好的效果,逐渐成为人们关注的焦点。氧化锌(ZnO)因具有优异的光化学性质、廉价易得、无毒无害、化学性质稳定等优点,作为光催化剂广泛应用于污染水体治理。但是,ZnO的宽带隙(Eg=3.37ev)阻碍了光激发,导致光响应范围窄,只能吸收紫外光,生成的电子-空穴对复合率高,难以回收再利用等缺陷限制了其发展。
铁酸锌是铁氧体的一种,它的化学分子式为ZnFe2O4,其带宽较窄(1.92eV),具有比较好的可见光响应能力,优异的光化学稳定性以及磁可分离的特性,在光、热、电、磁等领域都有很好的应用潜力,但它的光催化能力较弱,光量子效率低,不能将污染物进行有效的降解。如果将ZnFe2O4与ZnO复合,ZnFe2O4吸收可见光后发生电子跃迁,激发态的电子传输到ZnO的导带后导致ZnO的禁带宽度降低,使其可利用的可见光范围扩大,从而扩展了ZnO的光谱响应范围,从而提高光催化性能。
在材料科学领域中,复合材料在性能上取长补短,产生协同效应,在诸多领域如工业、生物医学领域等显示出极大的应用前景。将纳米ZnO和ZnFe2O4负载在有机或无机材料上,不仅可以扩展ZnO的光谱响应范围,提高光催化性能,还可以解决其制备过程中易团聚,应用中难分离等缺点。无机载体具有密度大(一般仅适用固定床反应器)的特点,限制了其在光催化工程中的应用;常用的有机聚合物载体如聚苯乙烯等,虽然克服了无机载体密度大的缺点,可适用于悬浮床反应器,但石油基聚合物不易降解和再生,环境友好性差。生物基有机材料进入人们的视线。周晓龙等将ZnO固定在再生纤维素上制备的纳米ZnO再生纤维素膜用于光降解甲基橙具有很好的效果。
桑枝木粉,主要成分为纤维素、半纤维素、木质素等,作为养蚕业的副产品,在我国都被焚烧或丢弃,造成严重的环境污染。据报道,纤维素上的羟基可以促进CuO等无机粒子成核、生长,负载在纤维素纤维表面。多糖类聚合物,如溶解的纤维素,淀粉等可促进纳米ZnO的生成。水热法是制备生物基纳米复合材料的有效方法之一。
发明内容
本发明要解决的技术问题是提供一种纳米氧化锌/铁酸锌/木粉三元复合材料,该材料在紫外光区和可见光区都有吸收,且稳定、环保易回收。本发明要解决的另一个技术问题是提供一种纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,所用溶剂NaOH/尿素价廉易得,原料桑枝木粉属于农林废弃物,可很好的实现废弃物资源化利用。本发明要解决的技术问题还有一个是提供一种纳米氧化锌/铁酸锌/木粉三元复合材料在可见光下光催化降解亚甲基蓝废水中的应用,光降解亚甲基蓝的去除效率大于98%;五次循环利用后,光催化降解率仍在90.0%以上。
为了解决上述问题,本发明所采用的技术方案如下:
一种纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,包括以下步骤:
(1)将纳米ZnFe2O4分散于无水乙醇中,再加入锌源,超声震荡,得到溶液A;ZnFe2O4中Zn与锌源中Zn的摩尔比为1∶6~1∶30;
(2)将桑枝木粉溶解于氢氧化钠尿素溶液中,搅拌,得到溶液B;所述桑枝木粉与氢氧化钠尿素溶液的质量比为1∶15~1∶25;
(3)将溶液A缓慢滴加到溶液B中,搅拌陈化,然后将混合溶液加入到水热反应釜中,进行水热反应,反应结束后过滤、水洗、烘干得到纳米氧化锌/铁酸锌/木粉三元复合材料;所述水热反应温度为90~130℃,反应时间为5~18h。
所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,所述锌源为醋酸锌。
所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,所述氢氧化钠尿素溶液中氢氧化钠、尿素和水的质量含量分别为7%、12%和81%。
所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,所述桑枝木粉低温溶解于氢氧化钠尿素溶液中,温度为-5~-15℃。
所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,所述桑枝木粉低温溶解于氢氧化钠尿素溶液中,桑枝木粉与氢氧化钠尿素溶液的质量比为1∶20~1∶25。
所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,所述溶液A和溶液B质量比为1∶1~2∶1。
所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,所述步骤(3),搅拌陈化的时间为30min。
上述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法制备得到的纳米氧化锌/铁酸锌/木粉三元复合材料。
上述纳米氧化锌/铁酸锌/木粉三元复合材料在光催化降解亚甲基蓝废水中的应用。
有益效果:与现有的技术相比,本发明的优点包括:
(1)本发明制备方法简单,以NaOH/尿素溶液为处理剂,将桑枝木粉部分溶解,不溶部分主要为纤维素,作为ZnO基复合材料的生物基载体;溶解的组分主要为半纤维素、小分子的纤维素等多糖类聚合物,作为纳米ZnO的促进剂;加入纳米铁酸锌,通过水热法原位合成来制备纳米ZnO基三元复合材料;所用溶剂NaOH/尿素价廉易得,原料桑枝木粉属于农林废弃物,可很好的实现废弃物资源化利用。
(2)本发明制备的氧化锌/铁酸锌/木粉三元复合材料在紫外和可见光区都有吸收,且稳定、环保易回收,在紫外和可见光照射下,光降解亚甲基蓝的去除效率大于98%。五次循环利用后,光催化降解率仍在90.0%以上,在作为光降解催化剂处理亚甲基蓝废水的处理方面,具有很好的实用性。
附图说明
图1为实施例1样品XRD图;
图2为实施例1样品UV-Vis DRS图;
图3为实施例1样品TG图;
图4为实施例1样品电镜图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合具体实施例对本发明的具体实施方式做详细的说明。
实施例1
氧化锌/铁酸锌/木粉三元复合材料的制备:称取0.0025mol的ZnFe2O4加入20mL无水乙醇中分散,再加入1mol/L的醋酸锌溶液30mL,超声振荡30min,此为溶液A;称取2g桑枝木粉低温(-10℃)溶解于50g氢氧化钠尿素溶液(7%NaOH∶12%Urea∶81%H2O)中,搅拌20min,形成溶液B。电动搅拌状态下,将溶液A缓慢滴加到溶液B中,搅拌陈化30min后,转移至100mL聚四氟乙烯内衬的不锈钢水热反应釜中,于100℃下水热反应12h,反应结束后取出。待反应釜自然冷却至室温,得到暗棕色沉淀,用蒸馏水洗6-8遍后,放入70℃烘箱中烘干,得到纳米氧化锌/铁酸锌/木粉三元复合材料。
图1为实施例1样品XRD图,在2θ=22°出有一个微弱的峰,是桑枝木粉中纤维素的特征峰。在2θ=31.8°、34.4°、36.3°、47.6°、56.7°、62.9°、66.4°等处峰是六方纤锌矿(标准卡片JCPDS CardNo.36-1451)的特征衍射峰,各个峰型尖锐,表明结晶良好。在2θ=29.9°、35.3°、56.6°、62.2°处的衍射峰分别对应ZnFe2O4的(220)、(311)、(511)和(440)晶面,对应铁酸锌的XRD标准卡片JCPDS CardNo.22-1012。从XRD图可见得到的复合材料中含有ZnO、ZnFe2O4和桑枝木粉,说明成功合成了三元复合材料。
图2紫外可见漫反射光谱图中可见(1.ZnO,2.ZnO/ZnFe2O4/木粉,3.ZnFe2O4),对照样ZnO在紫外区有光吸收,但在可见光区基本没有吸收。ZnFe2O4在可见光区有明显的吸收,从图2中可以看出,同时复合桑枝木粉与纳米ZnFe2O4后,复合材料的在紫外区的吸收与ZnO相比发生了较为明显的红移,光吸收范围拓宽到了可见光区,在紫外和可见光区都有吸收,420nm左右仍然有一个强的吸收峰。从图2中可见纳米ZnO/ZnFe2O4/木粉复合材料在可见光范围内的光吸收稍弱于紫外区,但已经表现出明显吸收,有利于其在光催化时利用光源中的可见光部分。
图3为热重分析曲线,100℃内的失重是由样品吸附的水分子汽化引起,导致重量逐渐下降约3%。100-420℃之间的失重是由桑枝木粉中的纤维素和木质素降解引起的。复合样品在约420℃之后TG曲线趋于平稳,不再有明显失重现象,此时样品中主要成分为纳米ZnO、纳米ZnFe2O4和少量的桑枝木粉中的灰分。桑枝木粉的TG曲线中最后残留的组分为灰分。根据TG图,结合实验条件,可估算复合材料中三元组分的质量比约为:ZnO∶ZnFe2O4∶桑枝木粉=48.2∶11.9∶39.9。
图4电镜图中铁酸锌纳米粒子覆盖在形状不规则的氧化锌纳米片上,分布不是很均匀,且纳米ZnO和ZnFe2O4结合紧密,大小不均一,直径在50-300nm。
实施例2
氧化锌/铁酸锌/木粉三元复合材料的制备:称取0.005mol的ZnFe2O4加入20mL无水乙醇中分散,再加入1mol/L的醋酸锌溶液30mL,超声振荡30min,此为溶液A;称取2g桑枝木粉低温(-10℃)溶解于50g氢氧化钠尿素溶液(7%NaOH∶12%Urea∶81%H2O)中,搅拌20min,形成溶液B。电动搅拌状态下,将溶液A缓慢滴加到溶液B中,搅拌陈化30min后,转移至100mL聚四氟乙烯内衬的不锈钢水热反应釜中,于100℃下水热反应12h,反应结束后取出。待反应釜自然冷却至室温,得到暗棕色沉淀,用蒸馏水洗6-8遍后,放入70℃烘箱中烘干,得到纳米氧化锌/铁酸锌/木粉三元复合材料。
实施例3
氧化锌/铁酸锌/木粉三元复合材料的制备:称取0.0025mol的ZnFe2O4加入20mL无水乙醇中分散,再加入1mol/L的醋酸锌溶液30mL,超声振荡30min,此为溶液A;称取2g桑枝木粉低温(-10℃)溶解于50g氢氧化钠尿素溶液(7%NaOH∶12%Urea∶81%H2O)中,搅拌20min,形成溶液B。电动搅拌状态下,将溶液A缓慢滴加到溶液B中,搅拌陈化30min后,转移至100mL聚四氟乙烯内衬的不锈钢水热反应釜中,于90℃下水热反应12h,反应结束后取出。待反应釜自然冷却至室温,得到暗棕色沉淀,用蒸馏水洗6-8遍后,放入70℃烘箱中烘干,得到纳米氧化锌/铁酸锌/木粉三元复合材料。
实施例4
氧化锌/铁酸锌/木粉三元复合材料的制备:称取0.0025mol的ZnFe2O4加入20mL无水乙醇中分散,再加入1mol/L的醋酸锌溶液30ml,超声振荡30min,此为溶液A;称取2g桑枝木粉低温(-10℃)溶解于50g氢氧化钠尿素溶液(7%NaOH∶12%Urea∶81%H2O)中,搅拌20min,形成溶液B。电动搅拌状态下,将溶液A缓慢滴加到溶液B中,搅拌陈化30min后,转移至100mL聚四氟乙烯内衬的不锈钢水热反应釜中,于100℃下水热反应14h,反应结束后取出。待反应釜自然冷却至室温,得到暗棕色沉淀,用蒸馏水洗6-8遍后,放入70℃烘箱中烘干,得到纳米氧化锌/铁酸锌/木粉三元复合材料。
实施例5
实施例1~4制备得到的纳米氧化锌/铁酸锌/木粉三元复合材料在作为光催化剂降解亚甲基蓝废水中应用,降解亚甲基蓝(MB,20mg/L)模拟废水,反应在光催化装置中进行,光源为20W紫外灯与日光灯,紫外光波长为254nm,光源与催化反应之间距离为10cm。100mg催化剂加入到50mL亚甲基蓝溶液中,避光搅拌30min,使其达到吸附平衡后,取样测定MB浓度,打开光源,搅拌2h后再次取样测定MB浓度。(MB浓度用紫外分光光度计在664nm测定。)根据去除率(Re)计算公式为Re%=(C0-C)*100%/C0。实施例1~4复合材料对亚甲基蓝的去除率结果如表1所示。由表1可知,本发明纳米氧化锌/铁酸锌/木粉三元复合材料对亚甲基蓝有很好的降解效果,去除率最高达到98.7%。
表1实施例1~4复合材料降解亚甲基蓝结果
复合材料 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
去除率/% | 98.7 | 98.4 | 75 | 86 |
实施例1中的复合材料回收后再次用于降解亚甲基蓝(MB,20mg/L),结果发现循环利用五次后MB去除率依然可以达到93.0%,说明本发明复合材料在作为光催化剂降解亚甲基蓝时有着很好的稳定性,可多次循环使用。
Claims (9)
1.一种纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,其特征在于,包括以下步骤:
(1)将纳米ZnFe2O4分散于无水乙醇中,再加入锌源,超声震荡,得到溶液A;所述ZnFe2O4中Zn与锌源中Zn的摩尔比为1∶6~1∶30;
(2)将桑枝木粉溶解于氢氧化钠尿素溶液中,搅拌,得到溶液B;所述桑枝木粉与氢氧化钠尿素溶液的质量比为1∶15~1∶25;
(3)将溶液A缓慢滴加到溶液B中,搅拌陈化,然后将混合溶液加入到水热反应釜中,进行水热反应,反应结束后过滤、水洗、烘干得到纳米氧化锌/铁酸锌/木粉三元复合材料;所述水热反应温度为90~130℃。反应时间为5~18h。
2.根据权利要求1所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,其特征在于,所述锌源为醋酸锌。
3.根据权利要求1所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,其特征在于,所述氢氧化钠尿素溶液中氢氧化钠、尿素和水的质量含量分别为7%、12%和81%。
4.根据权利要求1所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,其特征在于,所述桑枝木粉低温溶解于氢氧化钠尿素溶液中,温度为-5~-15℃。
5.根据权利要求1所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,其特征在于,所述桑枝木粉与氢氧化钠尿素溶液的质量比为1∶20~1∶25。
6.根据权利要求1所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,其特征在于,溶液A和溶液B质量比为1∶1~2∶1。
7.根据权利要求1所述纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法,其特征在于,所述步骤(3),搅拌陈化的时间为30min。
8.权利要求1所述的纳米氧化锌/铁酸锌/木粉三元复合材料的制备方法制备得到的纳米氧化锌/铁酸锌/木粉三元复合材料。
9.权利要求8所述的纳米氧化锌/铁酸锌/木粉三元复合材料在光催化降解亚甲基蓝废水中的应用。
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