CN110605129A - 一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法 - Google Patents
一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法 Download PDFInfo
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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Abstract
本发明公开了一种ZnTiO3半导体修饰改性Bi4NbO8Cl的复合光催化剂的简单制备方法。该方法以氧化铋、氯氧化铋和五氧化二铌为原料,通过球磨、煅烧合成了Bi4NbO8Cl;通过沉淀法制备得到了ZnTiO3;随后经过研磨、超声、煅烧的方法,制备得到ZnTiO3/Bi4NbO8Cl复合光催化剂。该实验方法比较安全可靠,操作简便。ZnTiO3与Bi4NbO8Cl呈现交叉带隙的特点,将两者复合后ZnTiO3可以作为能量的浅势捕获阱,使光生电子更容易从Bi4NbO8Cl的导带迁移到ZnTiO3的导带,光生空穴则更容易从ZnTiO3的价带迁移到Bi4NbO8Cl的价带,从而促进光生载流子的分离效率,进而提高复合催化剂的性能。
Description
技术领域:
本发明涉及一种无机复合改性光催化剂的制备方法,特别是涉及一种半导体复合改性材料的制备方法。更具体的说,是Bi4NbO8Cl作为主体,ZnTiO3去掺杂,两者通过机械方法进行混合,得到ZnTiO3改性Bi4NbO8Cl的复合光催化材料。本技术属于催化剂复合改性的制备领域。
背景技术:
21世纪以来,我国经济和科技水平迅速发展已跻身于世界前沿位置,与此同时导致我国出现了环境污染日益严重、能源逐渐枯竭的状况。其中水污染现象尤其严重,所以改善环境污染和合理利用能源已成为刻不容缓的事情。在过去的几十年中,光催化材料的研究主要集中在金属氧化物或氮氧化物上,但是这两类物质都有较大的缺点:对于金属氧化物,禁带宽度较大,能吸收的可见光频段仅占波谱的4%左右;对于氮氧化物,在阳光照射下不稳定且易分解。科学家们逐渐探索出用氯代替氮制备氯氧化物,其中Bi4NbO8Cl是具有代表性的该类光催化剂。Bi4NbO8Cl的带隙为2.39eV左右,对紫外光有较强的响应;此外,该类光催化剂有效作用时间长,对环境无污染等特点使其成为理想的光催化材料。虽然Bi4NbO8Cl作为光催化剂有一定的优势,但是在使用过程中仍存在以下两个问题:
(1)Bi4NbO8Cl的禁带较宽(2.39eV),只能吸收波长约在520nm以下的短波光,但低于387nm左右的偏紫外光能量只占太阳光能的5%。因此,如何扩大催化剂的可见光响应能力,是影响Bi4NbO8Cl能否大规模实际应用的一个重要因素。
(2)Bi4NbO8Cl作为单一的半导体材料,与改性催化剂相比,其光生载流子复合率仍然较高,较低的载流子分离效率一定程度上限制了Bi4NbO8Cl的实际应用。
为了解决上述问题,需要对Bi4NbO8Cl进行改性处理。Yong You[1]等人通过高能球磨法制备出了g-C3N4/Bi4NbO8Cl的复合材料,与纯g-C3N4和Bi4NbO8Cl 相比,光催化制氢的活性明显提高。魏志东[2]等人制备出了掺钇的 Bi4NbO8Cl/Nb2O5的新型异质结,同样可以提高光催化制氢的能力。ZnTiO3作为光催化剂的性能已经被大量实验证实,比如蒋正静[3]等人采用溶胶-凝胶法制备出了纳米级钛酸锌粉体,在紫外-可见光下降解活性红紫染料,30min后染料被光催化降解成无机小分子,证实了ZnTiO3-TiO2对水溶性染料光催化降解有较好的活性。但是目前还没有关于将Bi4NbO8Cl和ZnTiO3复合进行修饰改性,以提高光催化降解污染物的相关报道。
发明内容:
本发明的目的是提供一种对Bi4NbO8Cl进行修饰改性的制备方法,以克服目前单一Bi4NbO8Cl催化剂的性能不足问题。经多次探索,得出一种 ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,包含以下步骤:
1、一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于,按以下步骤进行:
(1)Bi4NbO8Cl的制备:按3:2:1的质量比称取氧化铋、氯氧化铋和五氧化二铌于玛瑙球磨罐中,加入一定体积的无水乙醇以及一定数量的玛瑙球后,以一定的转速球磨一段时间,取出混合液干燥,然后经过高温煅烧得到Bi4NbO8Cl粉末。所述步骤中Bi4NbO8Cl的制备,加入样品的总质量为6-36g,加入的无水乙醇为10-60mL,需要的玛瑙球直径为5-10mm,个数为20-100个。球磨转速为300r/min,球磨时间为2h。得到Bi4NbO8Cl粉末的高温煅烧温度为600℃,时间为10h。
(2)ZnTiO3的制备:将3.1mL钛酸丁酯溶于10mL无水乙醇中,形成溶液A;将1.5mL冰醋酸和2.75g六水合硝酸锌先后溶于10mL无水乙醇中,形成溶液 B;在搅拌状态下,将溶液B缓慢滴加到溶液A中,搅拌30min后陈化24h,随后在105℃下干燥12h,将得到的前驱体经过600℃煅烧3h后得到ZnTiO3粉末。
(3)ZnTiO3与Bi4NbO8Cl的复合:按一定的质量比称取一定量的ZnTiO3和Bi4NbO8Cl,研磨一段时间后,转移到烧杯中,加入一定量的无水乙醇,超声一段时间后干燥,将干燥后的粉末在一定温度下煅烧一定时间,得到 ZnTiO3/Bi4NbO8Cl复合光催化剂材料。
2、如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中ZnTiO3的质量分数是Bi4NbO8Cl的5%-30%。
3、如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中制备复合材料时研磨时间为5-60min。
4、如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中制备复合材料时加入无水乙醇的量为5-30mL。
5、如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中制备复合材料时超声时间为10-60min。
6、如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中将干燥后的粉末在马弗炉中的热处理温度为200-550℃,时间为0.5-3h,升温速率为2-8℃/min。
本发明的优点:
(1)本发明所采用的制备方法设备简单,成本较低,安全性高。
(2)ZnTiO3与Bi4NbO8Cl呈现交叉带隙的特点,将两者复合后ZnTiO3可以作为能量的浅势捕获阱,促进光生载流子的分离,减少光电流的产生,进而提高复合催化剂的性能。
附图说明:
图1,Bi4NbO8Cl、ZnTiO3和20%ZnTiO3/Bi4NbO8Cl(20%BZT)的XRD谱图
图2,20%ZnTiO3/Bi4NbO8Cl复合光催化剂的HRTEM图
图3,Bi4NbO8Cl、ZnTiO3和20%ZnTiO3/Bi4NbO8Cl(20%BZT)复合光催化剂的催化降解图
具体实施例一:
(1)Bi4NbO8Cl的制备:称取9gBi2O3、6gBiOCl和3gNb2O5先后溶于30ml无水乙醇中,放入玛瑙球磨罐中,放入50个直径为10mm的玛瑙球。将混合液在球磨机中球磨2h,转速为300r/min,将球磨后的混合液在60℃下干燥12h。干燥后的粉末经研磨后在600℃下煅烧10h,升温速率为5℃/min,得到亮黄色 Bi4NbO8Cl粉末。
(2)ZnTiO3的制备:将3.1mL钛酸丁酯溶于10mL无水乙醇中,形成溶液A;将1.5mL冰醋酸和2.75g六水合硝酸锌先后溶于10mL无水乙醇中,形成溶液B;在搅拌状态下,将溶液B缓慢滴加到溶液A中,搅拌30min后陈化24h,随后在105℃下干燥12h,将得到的前驱体经过600℃煅烧3h后得到ZnTiO3粉末。
(3)ZnTiO3与Bi4NiO8Cl的复合:分别称取0.4g Bi4NbO8Cl和0.08g的ZnTiO3粉末置于研钵中研磨10min后倒入烧杯中,加入10mL无水乙醇,超声30min 后,在60℃下干燥6h。将干燥后的粉末在300℃下热处理2h,升温速率为5℃ /min,得到20%ZnTiO3/Bi4NbO8Cl复合光催化剂,简化为20%BZT。
光催化性能测试是在室温条件下使用氙灯作为光源,并且将罗丹明B(RHB) 的降解速率作为评价指标。我们还设置了一个空白组作为对照实验,尝试改变 ZnTiO3掺杂量制得不同的复合催化剂。ZnTiO3的掺杂量分别为10%、20%、30%。,发现当掺杂量为20%时,复合非均相催化剂具有最佳性能。实验操作如下:在洁净的石英试管中加入0.05g的光催化剂和50mL、5mg/L的RHB溶液,使各个试管与光源的距离保持相等。黑暗中静置30min,以保证RHB在样品的表面吸附和解吸附达到平衡;然后打开循环冷却水、氙灯光源、搅拌器和公转旋钮,待光稳定后开始计时,进行300min的光照。光照过程中,每30min取样一次,取样体积约为3mL。将所取样品注入离心管中进行离心取出上层清液,测试该上清液在553nm处的吸光度。
从图1中可以看出:纯Bi4NbO8Cl在2θ=29°和32°处的衍射峰对应于标准卡片号No.84-0843的(116)和(020)晶面;纯ZnTiO3在2θ=35°和30°的衍射峰对应于标准卡片号No.39-0190的(311)和(220)晶面。掺杂ZnTiO3后,可以明显发现属于ZnTiO3的2θ=35°的峰出现在Bi4NbO8Cl/ZnTiO3的衍射图中。所以这说明Bi4NbO8Cl和ZnTiO3成功地复合在一起。从图2的局部放大图可以清晰地看到在Bi4NbO8Cl上附着ZnTiO3颗粒,其中Bi4NbO8Cl晶面间距0.254nm对应于(311)晶面;ZnTiO3晶面间距为0.375nm对应于(112)晶面,进一步证明可以成功地获得复合ZnTiO3/Bi4NbO8Cl。图3中C/C0用于评价样品的催化降解效率。在相同条件下,对于ZnTiO3,RHB的降解率约为65%,样品Bi4NbO8Cl 的降解率约为90%。Bi4NbO8Cl与ZnTiO3复合后,20%ZnTiO3/Bi4NbO8Cl复合催化剂的光催化效率较高,可以达到97%左右。所以说,我们制备的 ZnTiO3/Bi4NbO8Cl复合催化剂确实提高了Bi4NbO8Cl的光催化性能,也就是两者复合形成的异质结抑制了ZnTiO3/Bi4NbO8Cl体系中光生载流子的复合,从而提高了光催化活性。
参考文献
[1]You Y,Wang S,Xiao K,et al.Z-Scheme g-C3N4/Bi4NbO8Cl Heterojunctionfor Enhanced Photocatalytic Hydrogen Production[J].ACS Sustainable Chemistry&Engineering.2018,6,16219-16227.
[2]Zhidong W,Junying L,Wenjian F,et al.Enhanced photocatalytichydrogen evolution using a novel in situ heterojunction yttrium-dopedBi4NbO8Cl@Nb2O5[J]. International Journal of Hydrogen Energy,2018:14281-14292.
[3]蒋正静,唐果东,戴洁.纳米级钛酸锌粉的制备及其光催化染料降解的应用[J].光谱实验室,2002,19(5):593-595.
Claims (6)
1.一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于,按以下步骤进行:
(1)Bi4NbO8Cl的制备:按3:2:1的质量比称取氧化铋、氯氧化铋和五氧化二铌于玛瑙球磨罐中,加入一定体积的无水乙醇以及一定数量的玛瑙球后,以一定的转速球磨一段时间,取出混合液干燥,然后经过高温煅烧得到Bi4NbO8Cl粉末。所述步骤中Bi4NbO8Cl的制备,加入样品的总质量为6-36g,加入的无水乙醇为10-60mL,需要的玛瑙球直径为5-10mm,个数为20-100个。球磨转速为300r/min,球磨时间为2h。得到Bi4NbO8Cl粉末的高温煅烧温度为600℃,时间为10h。
(2)ZnTiO3的制备:将3.1mL钛酸丁酯溶于10mL无水乙醇中,形成溶液A;将1.5mL冰醋酸和2.75g六水合硝酸锌先后溶于10mL无水乙醇中,形成溶液B;在搅拌状态下,将溶液B缓慢滴加到溶液A中,搅拌30min后陈化24h,随后在105℃下干燥12h,将得到的前驱体经过600℃煅烧3h后得到ZnTiO3粉末。
(3)ZnTiO3与Bi4NbO8Cl的复合:按一定的质量比称取一定量的ZnTiO3和Bi4NbO8Cl,研磨一段时间后,转移到烧杯中,加入一定量的无水乙醇,超声一段时间后干燥,将干燥后的粉末在一定温度下煅烧一定时间,得到ZnTiO3/Bi4NbO8Cl复合光催化剂材料。
2.如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中ZnTiO3的质量分数是Bi4NbO8Cl的5%-30%。
3.如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中制备复合材料时研磨时间为5-60min。
4.如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中制备复合材料时加入无水乙醇的量为5-30mL。
5.如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中制备复合材料时超声时间为10-60min。
6.如权利要求1所述的一种ZnTiO3/Bi4NbO8Cl复合光催化剂材料的制备方法,其特征在于步骤(3)中将干燥后的粉末在马弗炉中的热处理温度为200-550℃,时间为0.5-3h,升温速率为2-8℃/min。
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