CN112473681A - 铋酸铜/氧化铈光催化剂的合成及其对甲苯、甲醛的净化 - Google Patents
铋酸铜/氧化铈光催化剂的合成及其对甲苯、甲醛的净化 Download PDFInfo
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Abstract
本发明属于环境工程领域的实用技术，提供一种CuBi2O4/CeO2复合光催化剂在太阳光下将室内外高浓度甲醛和甲苯净化处理。通过简单的溶剂热法和回流法制备出CeO2和CuBi2O4光催化剂，制备出在太阳光下高效氧化降解高浓度甲醛和甲苯的环境友好型复合催化剂。将少量的复合催化剂涂抹于表面皿上，在太阳光能量驱动下就可以将高浓度的甲醛和甲苯迅速分解转化，生成无毒无害的二氧化碳和水，且催化稳定性极高可以持久重复使用。所制得的催化剂无毒、无害、低成本，且便于投放使用和回收。符合环境净化的要求，有望应用于室内外高浓度挥发性空气污染物的净化领域。
Description
技术领域
本发明涉及一种新型光催化剂的合成方法及其在太阳光驱动、环境温度压力下对室内外甲苯和甲醛高效净化处理方面的应用，工程上涉及室内外气态污染物处理技术，技术上涉及材料合成领域及太阳光催化领域。
背景技术
挥发性有机化合物（VOC），尤其是工业产品（如粘胶，油漆，塑料，橡胶和汽油）中的苯系和醛系，经常释放到环境中，已成为最常见和最严重的空气污染物。为了有效消除有害的VOC，人们经常使用各种清洁方法，例如光催化，热催化，吸附和生物技术净化等技术。但是，在这些方法中的大多数对于去除气态甲苯（C7H8）（致癌和难分解的芳烃）都不是有效的或不经济的。例如，活性炭材料吸附所面临的主要问题包括吸附位点饱和和解吸再生等困难。而热催化氧化方法，即使使用贵金属催化剂（例如Au，Pt和Pd）作为催化剂，反应温度仍高于150 °C，这在实践中不方便大量应用，并且还会消耗大量能量。同时，生物技术在节能方面受到限制，并且在许多实际应用中特别是在气态挥发性有机化合物的去除方面带来不便。而太阳光驱动的光催化方法，在常温常压的简便条件下即可应用的高效绿色环保无次生污染的技术。
二氧化铈（CeO2）是一种多用途的催化材料，由于其易于调控形貌和好的电子传导性，可以有效的促进电子与空穴对的分离与转移。作为典型的缺陷类材料，在合成过程中很容易生成氧缺陷，有助于对气态甲苯和甲醛的吸附和催化氧化。同时，二氧化铈的禁带宽度较宽，具有很强的氧化还原性能。然而，宽的禁带宽度也导致只有紫外光才可以激发二氧化铈，很大程度上限制了其在光催化领域的应用。
铋酸铜光催化剂，具有较窄的禁带宽度，较强的光响应以及较宽光响应范围，可以充分利用太阳光谱的可见光区域。为了拓宽二氧化铈在光催化氧化VOC的应用，通过与铋酸铜（CuBi2O4）光催化剂复合形成异质结CuBi2O4/CeO2，可有效提升光响应范围，更充分地利用了太阳光，异质结的形成还可可有效地分离光生电子和空穴对，降低载流子的复合率，对室内甲醛和甲苯起到高效催化降解的功能。
本发明制备了新型CuBi2O4/CeO2异质复合相光催化剂，并应用于室内外高浓度VOC(甲醛和甲苯)的净化处理，制备方便，操作简单，用量少，可持久重复利用。对高浓度的甲苯和甲醛都具有很好的光降解作用，且CO2生成效率和矿化效率高，达到净化处理室内外挥发性污染物的目的，可推广至室内外空气净化领域。
发明内容
对于室内外高浓度甲醛与甲苯的净化去除，如今大家普遍使用的方法是绿植吸附、活性炭净化、物理通风等主要吸附类的物理方法。虽然这些方法能在一定程度上降低污染物浓度，但也并未将挥发性污染物分解为无害的CO2，H2O等物质，同时容易达到饱和状态而不能继续吸附，难以实现易于脱附和循环利用，还会脱附释放出污染物从而形成二次污染等未解决难题。本发明针对室内外VOC的污染，合成制备CuBi2O4/CeO2复合光催化剂，开发了可以高效利用可见光，将高浓度的甲醛与甲苯彻底氧化为无害的二氧化碳和水，而且具有很高的稳定性，可以多次循环利用的催化剂。本发明具有对高浓度甲醛与甲苯的高效催化效果，制作简单，使用条件简单，可以推广至室内外空气净化领域，具有很高的应用价值。
本发明的具体技术方案如下：
二氧化铈（CeO2）的制备：CeO2通过沉淀法制备。由35 mL蒸馏水和35 mL乙二醇组成的溶液，在25 °C下机械搅拌1 小时后，将0.525 g一水合柠檬酸药物和0.4929 g无水三氯化铈（CeCl3），连续搅拌下将其完全溶解后，转移到衬有聚四氟乙烯的不锈钢高压釜中，在180 °C下水热反应12小时。高压釜冷却至环境温度后，通过用水和无水乙醇洗涤几次获得白色的Ce(OH)3前驱体粉末，最后在75 °C下干燥10 h至完全干燥。然后，在管式炉中空气氛围下550°C煅烧Ce(OH)3前驱体5小时获得最终的黄色CeO2粉末。
铋酸铜（CuBi2O4）的制备：将1.9402克五水合硝酸铋（Bi(NO3)3·5H2O）溶解于20 mL浓硝酸溶液中，在室温下连续搅拌30分钟达到充分溶解，标记为溶液A。在20 mL超纯水中加入0.4832 g三水合硝酸铜（Cu(NO3)2·6H2O）和1.26 g一水合柠檬酸（C6H8O7·H2O）后连续搅拌30分钟搅拌，标记为溶液B。另外，将9.6 g氢氧化钠（NaOH）溶解于20mL超纯水，搅拌至完全溶解变透明溶液，标记为溶液C。在剧烈机械搅拌下，将溶液B、溶液A中和溶液C混合，转移到100 mL三口圆底烧瓶中，加热到90 °C下保持5小时后溶液将变成黑褐色。充分干燥后，在管式炉中空气氛围下550°C煅烧前驱体1小时获得最终的褐色CuBi2O4粉末。
复合催化剂CuBi2O4/CeO2的合成：将合成好的一定量CuBi2O4溶解在35 mL超纯水中，通过超声方法将CuBi2O4充分破碎后，再加入35 mL乙二醇按照合成CeO2的步骤一步一步合成出CuBi2O4/CeO2复合催化剂。
附图说明
图1为CuBi2O4/CeO2复合光催化材料的XRD 图。
图2为CuBi2O4/CeO2复合光催化材料的SEM图。
图3为CuBi2O4/CeO2复合光催化材料的FT-IR图。
图4为CuBi2O4/CeO2复合光催化材料的甲苯降解曲线图和CO2生成率图。
图5为CuBi2O4/CeO2复合光催化材料的甲醛降解曲线图和CO2生成率图。
具体实施方式
以下结合实施例对本发明进一步说明。
实施例：首先，将30 mg复合催化剂使用无水乙醇充分分散涂抹在表面皿上，放进反应器后通过加热器将反应器和各个连接管路保温于80 °C，保证甲醛或甲苯的气态气氛。之后，通过配气系统将一定量的气态甲苯或甲醛用空气带进反应器，由光声红外检测仪内置气体泵达到气体循环的目的。光源选用的300w氙灯，由上到下的垂直照射模式。甲苯或甲醛气体降解浓度和CO2气体生成量由光声红外检测仪自动检测并每10分钟出一次数据。
图4为CuBi2O4/CeO2复合光催化材料的甲苯降解曲线图和CO2生成率图。
图5为CuBi2O4/CeO2复合光催化材料的甲醛降解曲线图和CO2生成率图。
以上所述，仅为本发明较好的具体实施方案，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。
Claims (6)
1.一种复合光催化剂（CuBi2O4/CeO2）材料的制作方法，其特征在于，包括以下几种步骤：
步骤一：通过沉淀法制备表面富缺陷的CeO2；
由35 mL蒸馏水和35 mL乙二醇组成的溶液，将0.525 g一水合柠檬酸药物溶解到以上70 mL混合溶液中；
再加入0.4929 g无水三氯化铈（CeCl3），将混合物转移到衬有聚四氟乙烯的不锈钢高压釜中，在180 °C下进行水热反应12小时；
高压釜冷却至环境温度后，通过用水和无水乙醇洗涤几次获得白色的Ce(OH)3前驱体粉末，最后在75 °C下干燥10 h至完全干燥；
然后，在管式炉中空气氛围下550 °C煅烧Ce(OH)3前驱体5小时获得最终的黄色CeO2粉末；
步骤二：铋酸铜（CuBi2O4）的制备：将1.9402 g五水硝酸铋（Bi(NO3)3·5H2O）溶解于20mL稀硝酸溶液中，标记为溶液A；
在20 mL超纯水中加入0.4832 g三水合硝酸铜（Cu(NO3)2·6H2O）和1.26 g一水柠檬酸（C6H8O7·H2O），标记为溶液B；
将9.6 g氢氧化钠（NaOH）溶解于20 mL超纯水，搅拌至完全溶解变透明溶液，标记为溶液C；
将溶液A、溶液B和溶液C混合，将溶液转移到100 mL三口圆底烧瓶中，加热到90 °C下保持5小时后溶液将变成黑褐色；
反应完成后，用水和乙醇洗涤几次获得CuBi2O4前驱体粉末，然后在80 °C下干燥10 h至完全干燥；
充分干燥后，在管式炉中空气氛围下550 °C煅烧前驱体1小时获得最终的褐色CuBi2O4粉末；
步骤三：复合催化剂CuBi2O4/CeO2的合成：将合成好的一定量CuBi2O4溶解在35mL超纯水中，通过超声方法将CuBi2O4充分破碎后，再加入35mL乙二醇按照合成CeO2的步骤一步一步合成出CuBi2O4/CeO2复合催化剂；
步骤四：首先，将30 mg复合催化剂使用无水乙醇充分分散涂抹在表面皿上，放进反应器后通过加热器将反应器和各个连接管路保温于80 °C，保证甲醛或甲苯的气态气氛；
之后，通过配气系统将一定量的气态甲苯或甲醛用空气带进反应器，由光声红外检测仪内置气体泵达到气体循环的目的；
光源选用的300 w氙灯，由上到下的垂直照射模式；
甲苯或甲醛气体降解浓度和CO2气体生成量由光声红外检测仪自动检测并每10分钟出一次数据。
2.根据权利要求1所述的无水三氯化铈、乙二醇、一水合柠檬酸、无水乙醇、五水合硝酸铋、浓硝酸、三水合硝酸铜、氢氧化钠、甲苯、甲醛溶液均为分析纯。
3.根据权利要求1所述的制备过程，其特征在于，乙二醇和水的比例是CeO2样品形貌调控的关键，并且乙二醇的加入会使CeO2样品形成氧缺陷，提高纯相CeO2的催化活性和吸附性能；高温煅烧CuBi2O4样品有利于提高结晶性，使其在催化氧化反应中更加稳定存在。
4.根据权利要求1所述的复合催化剂的的反应条件，其特征在于，反应条件模拟室内外挥发性有害气体环境。
5.根据权利要求1所述的复合催化剂的的反应条件，其特征在于，通过模拟太阳光将高浓度甲苯和甲醛氧化为无害的二氧化碳和水，CO2生成率高达87.62%和92.11%。
6.根据权利要求1，3，4，5所述的二元催化剂处理室内甲醛与甲苯，其特征在于，配置模拟室内外挥发性气体环境，甲醛初始浓度为10000 ppm，甲苯初始浓度为1800 ppm，催化剂投入量为30毫克，将300W氙灯光源垂直照射于催化剂表面，使用500 mL体积的反应容器，反应容器和气体管路保温温度为80 °C，使用光声光谱仪同步检测VOCs浓度和CO2生成量，辅以光声光谱仪内置空气循环泵，光照2小时后，甲醛和甲苯的降解率均达到100%，CO2生成率分别为甲醛92.11%和甲苯87.62%。
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