CN111036189B - 活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法 - Google Patents
活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法 Download PDFInfo
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Abstract
本发明涉及活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,属于光催化剂技术领域。本发明将铜盐和锌盐溶解于去离子水中得到混合溶液A,再将活性炭分散到混合溶液A中并超声震荡预处理10~35min得到混合液B;将强碱溶液逐滴滴加到混合液B中使体系不再析出沉淀,静置老化1.5~3h得到前驱体;将前驱体置于温度为100~180℃条件下水热反应10~13h,固液分离,固体烘干即得活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体。本发明制备的活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体,负载均匀,ZnO/CuO或ZnO/CuO/Cu2O的粒度为28~60nm,70min降解MB污染物效率达到99.8%,且制备过程由一步水热合成,操作简便、成本低,利用了大麻杆活性炭,环境友好。
Description
技术领域
本发明涉及活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,属于光催化剂技术领域。
背景技术
光催化技术作为一种将太阳能转化为化学能的绿色技术,因其具有降解效率高、无污染、可重复利用和节能环保等优异性能,在解决环境污染问题方面具有极大的应用发展前景。半导体材料是光催化技术的重要研究内容,制备一种光电性能优良、无毒无害、高稳定性、高催化活性及价格低廉的光催化剂成为当前研究热点。
ZnO是目前最常用的半导体光催化剂之一,具有价格低廉,反应条件温和,稳定性高等优点,但由于ZnO能隙宽(3.37ev),只对紫外光响应,进行反应时光生载流子分离率低,同时还伴随着光化学腐蚀现象发生,限制了其实际应用。为了克服这些缺点,提高ZnO 的利用率,一般采用化学沉淀法、溶胶-凝胶法、模板法对ZnO进行贵金属掺杂,合成Ag/ZnO、Pd/ZnO、Pt-ZnO等复合光催化剂,避免ZnO 发生光化学腐蚀,提高催化剂的稳定性,拓宽了可见光的吸收,但成本太高;或采用水热法、化学喷雾热解技术合成二元催化剂ZnO/TiO2、ZnO /Fe2O3、ZnO/Cu2O,但普遍存在工艺繁琐、对可见光响应范围较窄、催化性能不能达到最佳、环境不友好等缺点。
发明内容
针对上述现有技术存在的问题及不足,本发明提供活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,本发明制备的以活性炭为载体的ZnO/CuO或ZnO/CuO/Cu2O光催化剂,在光催化过程中, ZnO在光照下产生的电子-空穴对与H2O、O2等反应生成羟基自由基、过氧自由基等具有强氧化还原性的物质,可将有机污染物降解成水、CO2和其他无机小分子物质。在“活性炭(AC)-ZnO-铜的氧化物”催化机制中,活性炭迅速吸附污染物转移到ZnO表面,产生浓度差以提高光催化效率;铜的氧化物其能隙小于ZnO,与ZnO的协同作用降低光生电子—空穴的复合,提高催化剂的效率。
活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,具体步骤如下:
(1)将铜盐和锌盐溶解于去离子水中得到混合溶液A,再将活性炭分散到混合溶液A中并超声震荡预处理10~35min得到混合液B;
(2)将强碱溶液逐滴滴加到步骤(1)混合液B中使体系不再析出沉淀,静置老化1.5~3h得到前驱体;
(3)将步骤(2)前驱体置于温度为100~180℃条件下水热反应10~13h,固液分离,固体烘干即得活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体。
所述步骤(1)锌盐中Zn2+与铜盐中Cu2+的摩尔比为1~3:1,锌盐中Zn2+与活性炭中AC的摩尔比为1~3:1。
进一步地,所述锌盐为硝酸锌或醋酸锌,铜盐为硝酸铜或醋酸铜,活性炭为大麻杆活性炭。
优选的,大麻杆活性炭依据申请号为201810790146.9的专利“一种大麻杆活性炭的制备方法”中记载的方法制备而得。
所述步骤(1)超声震荡频率为35~50KHz。
所述步骤(2)强碱溶液为KOH、NaOH或四甲基碳酸氢铵溶液,强碱溶液浓度为0.5~2mol/L。
进一步地,所述烘干温度为60~80℃,烘干时间为6~10h。
本发明的有益效果是:
(1)本发明采用大麻杆活性炭为载体制备活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体,其比表面积达到2116.06m2/g,孔径尺寸1~3nm,吸附能力强,化学性质稳定;
(2)本发明采用的ZnO/CuO或ZnO/CuO/Cu2O的复合,利用铜的氧化物能隙小于ZnO,光催化过程中与ZnO的协同作用,降低光生电子-空穴对的复合;
(3)本发明制备的活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的催化活性高,对光谱范围从200nm~800nm的紫外光-可见光有较强吸收,大幅提高了太阳光的利用率,且稳定性优越;
(4)本发明一步水热法得到三元复合光催化复合粉体,在“活性炭(AC)-ZnO-铜的氧化物”催化机制中,活性炭迅速吸附污染物转移到ZnO表面,产生浓度差以提高光催化效率;铜的氧化物其能隙小于ZnO,与ZnO的协同作用降低光生电子-空穴的复合,提高催化剂的效率。
附图说明
图1为实施例1和2中复合粉体光催化剂的XRD图;
图2为实施例1和2中复合粉体光催化剂的SEM图;
图3为实施例1中复合粉体光催化剂的紫外-可见漫反射光谱(UV-vis)图;
图4为实施例1中的复合粉体光催化剂的降解效率图。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:活性炭负载ZnO/CuO光催化复合粉体的制备方法,具体步骤如下:
(1)将铜盐(硝酸铜Cu(NO3)2·3H2O)和锌盐(硝酸锌Zn(NO2)·6H2O)溶解于去离子水中得到混合溶液A,再将大麻杆活性炭分散到混合溶液A中并超声震荡预处理10min得到混合液B;其中锌盐(硝酸锌Zn(NO2)·6H2O)中Zn2+与铜盐(硝酸铜Cu(NO3)2·3H2O)中Cu2+的摩尔比为1:1,锌盐(硝酸锌Zn(NO2)·6H2O)中Zn2+与活性炭中AC的摩尔比为1:1,超声震荡频率为50KHz;
(2)将强碱溶液(KOH水溶液)以120滴/min的滴定速率逐滴滴加到步骤(1)混合液B中使体系不再析出沉淀,静置老化1.5h得到前驱体;其中强碱溶液(KOH水溶液)浓度为1mol/L;
(3)将步骤(2)前驱体转移至容量为100mL反应釜中,在温度为160℃的鼓风干燥箱中水热反应12h,冷却至室温,固液分离,固体置于温度为 60℃下烘干 10h即得活性炭负载ZnO/CuO光催化复合粉体;
本实施例活性炭负载ZnO/CuO光催化复合粉体的XRD图见图1,从图1可知,产物为氧化锌和氧化铜,氧化锌为稳定的六角纤锌矿结构,氧化铜为单斜晶体结构,且ZnO和CuO的结晶度发育较好;
本实施例活性炭负载ZnO/CuO光催化复合粉体的SEM形貌表征,如图2(a)所示,与纯的ZnO相比,所得的复合粉体形貌发生改变,出现了团簇状的ZnO/CuO,片状的活性碳上负载片状的ZnO,较小粒径的CuO负载在片状的ZnO上,纳米片的厚度粒径在40~60nm。通过对复合粉体的紫外可见漫反射光谱分析可知,在可见光区域有较强的吸收,吸收光谱可达到800nm(见图3);
取50mg本实施例制备的活性炭负载ZnO/CuO光催化复合粉体放入100mL浓度为27mg/L的亚甲基蓝(MB)溶液中,在自然光照射下照射1.5h(上午09:00~10:00),70min后催化效率可达到99.8%,重复降解5次降解率为95.8%(见图4)。
实施例2:活性炭负载ZnO/CuO/Cu2O光催化复合粉体的制备方法,具体步骤如下:
(1)将铜盐(醋酸铜Cu(CH3COO)2·H2O)和锌盐(醋酸锌 Zn(CH3COO)2)溶解于去离子水中得到混合溶液A,再将大麻杆活性炭分散到混合溶液A中并超声震荡预处理15min得到混合液B;其中锌盐(醋酸锌 Zn(CH3COO)2)中Zn2+与铜盐(醋酸铜Cu(CH3COO)2·H2O)中Cu2+的摩尔比为1:1,锌盐(醋酸锌 Zn(CH3COO)2)中Zn2+与活性炭中AC的摩尔比为1.2:1,超声震荡频率为35KHz;
(2)将强碱溶液(NaOH水溶液)以100滴/min的滴定速率逐滴滴加到步骤(1)混合液B中使体系不再析出沉淀,静置老化3 h得到前驱体;其中强碱溶液(NaOH水溶液)浓度为2mol/L;
(3)将步骤(2)前驱体转移至容量为100mL反应釜中,在温度为130℃的鼓风干燥箱中水热反应12h,冷却至室温,固液分离,固体置于温度为 80 ℃下烘干 6 h即得活性炭负载ZnO/CuO/Cu2O光催化复合粉体;
本实施例活性炭负载ZnO/CuO/Cu2O光催化复合粉体的XRD图见图2,从图2可知,产物为氧化锌、氧化铜和氧化亚铜;由XRD检测结果,通过JADE分析计算得到物相含量结果为:以质量百分数计,ZnO 51.6305%、CuO 44.7744%、Cu2O 3.5951%;
本实施例活性炭负载ZnO/CuO/Cu2O光催化复合粉体的SEM形貌表征,如图2(b)所示,活性炭负载ZnO/CuO/Cu2O光催化复合粉体为片状或块状活性碳上负载片状的ZnO,较小粒径的CuO/Cu2O负载在片状的ZnO上,与纯的ZnO相比,活性炭负载的ZnO沿(101)择优生长为纳米片;
取50mg本实施例制备的活性炭负载ZnO /CuO/Cu2O光催化复合粉体放入100mL浓度为27mg/L的亚甲基蓝(MB)溶液中,在自然光照射下照射1.5h(09:00~10:30),复合粉体的光催化70min降解率为100%,重复回收使用5次后,降解效率达到95.3%以上。
实施例3:活性炭负载ZnO/CuO光催化复合粉体的制备方法,具体步骤如下:
(1)将铜盐(硝酸铜Cu(NO3)2·3H2O)和锌盐(醋酸锌 Zn(CH3COO)2)溶解于去离子水中得到混合溶液A,再将大麻杆活性炭分散到混合溶液A中并超声震荡预处理20min得到混合液B;其中锌盐(醋酸锌 Zn(CH3COO)2)中Zn2+与铜盐(硝酸铜Cu(NO3)2·3H2O)中Cu2+的摩尔比为1:1,锌盐(醋酸锌 Zn(CH3COO)2)中Zn2+与活性炭中AC的摩尔比为3:1,超声震荡频率为30KHz;
(2)将强碱溶液(NaOH水溶液)以120滴/min的滴定速率逐滴滴加到步骤(1)混合液B中使体系不再析出沉淀,静置老化2h得到前驱体;其中强碱溶液(NaOH水溶液)浓度为1mol/L;
(3)将步骤(2)前驱体转移至容量为100mL反应釜中,在温度为180℃的鼓风干燥箱中水热反应10h,冷却至室温,固液分离,固体置于温度为75 ℃下烘干 8 h即得活性炭负载ZnO/CuO光催化复合粉体;
本实施例活性炭负载ZnO/CuO光催化复合粉体的XRD图可知,产物为氧化锌和氧化铜,氧化锌为六角纤锌矿结构,氧化铜为单斜晶体结构,且ZnO和CuO 的结晶度发育较好;
本实施例活性炭负载ZnO/CuO光催化复合粉体的SEM形貌表征可知,活性炭负载ZnO/CuO光催化复合粉体为片状或块状活性碳上负载片状的ZnO,较小粒径的CuO负载在片状的ZnO上,与纯的ZnO相比,活性炭负载的ZnO沿(101)择优生长为纳米片;
取30mg本实施例制备的活性炭负载ZnO /CuO光催化复合粉体放入100mL浓度为10mg/L的亚甲基蓝(MB)溶液中,在自然光照射下照射1.5h(09:00~10:30),复合粉体的光催化70min降解率为100%,重复回收使用5次后,降解效率达到94.7%以上。
实施例4:活性炭负载ZnO/CuO光催化复合粉体的制备方法,具体步骤如下:
(1)将铜盐(硝酸铜Cu(NO3)2·3H2O)和锌盐(硝酸锌Zn(NO2)·6H2O)溶解于去离子水中得到混合溶液A,再将大麻杆活性炭分散到混合溶液A中并超声震荡预处理20min得到混合液B;其中锌盐(硝酸锌Zn(NO2)·6H2O)中Zn2+与铜盐(硝酸铜Cu(NO3)2·3H2O)中Cu2+的摩尔比为2.5:1,锌盐(硝酸锌Zn(NO2)·6H2O)中Zn2+与活性炭中AC的摩尔比为1.2:1,超声震荡频率为50KHz;
(2)将强碱溶液(NaOH水溶液)以120滴/min的滴定速率逐滴滴加到步骤(1)混合液B中使体系不再析出沉淀,静置老化2h得到前驱体;其中强碱溶液(NaOH水溶液)浓度为1.5mol/L;
(3)将步骤(2)前驱体转移至容量为100mL反应釜中,在温度为160℃的鼓风干燥箱中水热反应10h,冷却至室温,固液分离,固体置于温度为 70 ℃下烘干 10 h即得活性炭负载ZnO/CuxO光催化复合粉体;
本实施例活性炭负载ZnO/CuO光催化复合粉体的XRD图可知,产物为氧化锌和氧化铜,氧化锌为六角纤锌矿结构,氧化铜在PDF卡片中的32.5°, 35.5°,38.7°,48.7°, 53.4°,58.3°, 61.5°, 66.2°, 68.1°, 72.4°,75.2°与(1 1 0), (0 0 2), (1 1 1), (2 ),(0 2 0), (2 0 2),(1 1), (3 1 ), (2 2 0), (3 1 1) ,(2 2 )晶面相对应;
本实施例活性炭负载ZnO/CuO光催化复合粉体的SEM形貌表征可知,活性炭负载ZnO/CuxO光催化复合粉体为为块状活性碳上负载棒状的ZnO,较小粒径的CuO负载在棒状的ZnO上,活性炭负载的ZnO沿(101)择优生长为纳米片;通过对复合粉体的紫外可见漫反射光谱分析可知,在可见光区域有较强的吸收,吸收光谱可达到800nm;
取50mg本实施例制备的活性炭负载ZnO /CuO光催化复合粉体放入100mL浓度为27mg/L的亚甲基蓝(MB)溶液中,在自然光照射下照射1.5h(09:00~10:30),复合粉体的光催剂70min降解率为99.8%,重复回收使用4次后,降解效率达到95.3%以上。
本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下做出各种变化。
Claims (5)
1.活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,其特征在于,具体步骤如下:
(1)将铜盐和锌盐溶解于去离子水中得到混合溶液A,再将活性炭分散到混合溶液A中并超声震荡预处理10~35min得到混合液B;其中锌盐中Zn2+与铜盐中Cu2+的摩尔比为1~3:1;
(2)将强碱溶液逐滴滴加到步骤(1)混合液B中使体系不再析出沉淀,静置老化1.5~3h得到前驱体;其中强碱溶液为KOH、NaOH或四甲基碳酸氢铵溶液;
(3)将步骤(2)前驱体置于温度为100~180℃条件下水热反应10~13h,固液分离,固体烘干即得活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体。
2.根据权利要求1所述活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,其特征在于:步骤(1)锌盐中Zn2+与活性炭中AC的摩尔比为1~3:1。
3.根据权利要求2所述活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,其特征在于:锌盐为硝酸锌或醋酸锌,铜盐为硝酸铜或醋酸铜,活性炭为大麻杆活性炭。
4.根据权利要求1所述活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,其特征在于:步骤(1)超声震荡频率为35~50KHz。
5.根据权利要求1所述活性炭负载ZnO/CuO或ZnO/CuO/Cu2O光催化复合粉体的制备方法,其特征在于:步骤(2)强碱溶液浓度为0.5~2mol/L。
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