CN114011445A - 一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法及应用 - Google Patents
一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法及应用,涉及光催化纳米材料制备与光催化分解水产氢领域。一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法包括:采用二氧化硅作模板剂,通过水热法制备硫化镉,再通过热碱液去除二氧化硅,制备空心结构的硫化镉;在氮气气氛下,通过焙烧法制备镍钴磷;经浸渍法将NiCoP负载到空心球CdS表面从而合成空心球硫化镉/镍钴磷异质结光催化剂。采用本发明方法制备的空心球硫化镉/镍钴磷异质结光催化剂结晶良好,通过形成异质结结构的方式增强了光生载流子的分离和传输效率,其可用于光催化水解产氢,光催化水解产氢活性更高,产氢速率更快。
Description
技术领域
本发明属于光催化纳米材料制备与光催化分解水产氢技术领域,具体涉及一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法及应用。
背景技术
目前,能源短缺和环境污染是人类面临的两项重大问题。传统化石能源消耗一方面是不可持续的,另一方面会带来SO2、NOx等环境污染问题,同时还会增加CO2的排放带来温室效应。寻求代替化石燃料的清洁能源是从根本上解决上述问题的突破口。光催化技术自发现以来备受人们的关注,光催化分解水产氢技术无疑是清洁利用太阳能的方式之一。开发高效的光催化剂一直科学界的目标之一。
硫化镉是一种典型的窄带隙光催化剂,有合适的能带位置、较高的发光效率,能用于可见光催化水解产氢。作为过渡金属硫化物,硫化镉具有价格低廉、性能稳定、无毒副作用、无二次污染、安全等优点。因为这些优点,硫化镉是极具潜力的光催化分解水产氢的催化剂,已经引起越来越多科研工作者的注意。然而,其仍然存在一些缺点:如载流子分离效率低、光催化水解产氢活性较低,存在光腐蚀等问题。
大量实验证明,形貌控制和构建异质结能有效提升光生载流子的分离效率,从而提升光催化产氢活性。两种不同的半导体相接触形成的界面区域即是异质结,以p-n异质结为例,当两种半导体材料接触,异质结两边的费米能级要趋于一致,引起电荷流动,导致界面的附近形成空间电荷区、内建电场。在内建电场的作用下,载流子会迅速分离从而减少载流子的复合几率。若异质结是非p-n结,则载流子依旧可以分离,这时的驱动力则是能级电势差。因此,考虑在硫化镉的基础上构建异质结,提高光生载流子分离效率进而提高光催化分解水产氢效率。
发明内容
为解决现有技术中存在的问题,本发明提供了一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法及应用,本发明方法制备工艺简单,成本低廉,制得的光催化剂光催化水解产氢活性优异。
为实现上述目的,本发明提供了一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法,制备步骤如下:
S1.将SiO2分散到去离子水中,再加入Cd(CH3COO)2·2H2O、CH4N2S(硫脲)进行搅拌,形成混合溶液;
S2.将混合溶液转移到100mL带不锈钢外壳的聚四氟乙烯反应釜中,进行水热反应,反应结束后自然冷却至室温;
S3.用去离子水和无水乙醇对步骤S2水热反应后的固体物质进行洗涤,再烘干;
S4.将步骤S3烘干后的固体物质放入热碱液中反应,反应过程中可去除SiO2,充分反应后,取出固体产物,并用去离子水和无水乙醇洗涤,烘干后制得空心球硫化镉;
S5.取适量NiCl2·6H2O、CoCl2·6H2O和NaH2PO2·H2O放入研钵中研磨,研磨后焙烧,即得镍钴磷;
S6.取适量步骤S4制得的空心球硫化镉与步骤S5制得的镍钴磷分散到无水乙醇中,再超声、搅拌;
S7.将步骤S6超声搅拌后的固体产物烘干,即得空心球硫化镉/镍钴磷异质结光催化剂。
进一步,步骤S1中,SiO2为直径200~500nm的纳米球结构,使用量为5~100mg;Cd(CH3COO)2·2H2O与CH4N2S的摩尔比为1:(1~4)。
进一步,步骤S4中,热碱液为50~500g/L的NaOH溶液,反应温度为90℃,反应时间为3h。
进一步,步骤S5中,NiCl2·6H2O、CoCl2·6H2O、NaH2PO2·H2O的摩尔比为0.7:0.3:3。
进一步,步骤S6中,镍钴磷与空心球硫化镉的质量比为(1~20):100。
按照本发明方法制备的空心球硫化镉/镍钴磷异质结光催化剂,可应用于光催化分解水产氢。
本发明的有益效果:
1、本发明方法使用的原料均为常用化学试剂,且来源广泛,价廉易得;同时反应设备简单,反应条件温和,通过简单的水热法和浸渍法便能制备空心球硫化镉/镍钴磷异质结光催化剂。
2、采用本发明方法制备的空心球硫化镉/镍钴磷异质结光催化剂光生载流子分离效率高、光致发光低。
3、采用本发明方法制备的空心球硫化镉/镍钴磷异质结光催化剂的光催化分解水产氢活性有较大提高。
附图说明
图1为实施例1~3以及对比例1~2的光催化分解水产氢活性速率图;
图2为实施例1~3以及对比例1~2的XRD图;
图3为对比例1、2的扫描电子显微镜图;
图4为实施例2以及对比例1~2的光致发光光谱图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是说明本发明,而非限制本发明。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
制备空心球硫化镉:在室温条件下,精确称取50mg的SiO2超声分散于75mL去离子水中,SiO2为直径200nm的纳米球,超声20min后得混合液A,然后称取1.067g Cd(CH3COO)2·2H2O和1.140g CH4N2加入到混合液A中,搅拌30min得到混合液B;之后将混合液B转移至100mL带不锈钢外壳的聚四氟乙烯反应釜中,在180℃下反应18h,反应结束,待反应釜自然冷却至室温后,取出反应后的固体样品并用去离子水和乙醇离心洗涤,离心产物在60℃下干燥,制得固体A;将固体A加入到100g/mLNaOH溶液当中,于90℃恒温水浴并搅拌3h,反应结束后,将所得固体样品用去离子水和乙醇离心洗涤,烘干后得到空心球硫化镉。
制备镍钴磷:称取0.30g CoCl2·6H2O、0.70g NiCl2·6H2O和1.34g NaH2PO2·H2O置于研钵中研磨均匀,再将研磨后的混合物转移至管式炉中,在氮气气氛下以1℃/min速度升温至350℃,在该温度下反应2h,反应结束后冷却至室温,即得镍钴磷。
制备空心球硫化镉/镍钴磷异质结光催化剂:称取30mg镍钴磷和0.5g空心球硫化镉加入50mL无水乙醇中,先超声3h,再搅拌24h得到混合液C,将混合液C于60℃下干燥,制得空心球硫化镉/镍钴磷异质结光催化剂,标记为HCS/NCP6。
实施例2
本实施例空心球硫化镉/镍钴磷异质结光催化剂的制备步骤与实施例1相同,但本实施例制备空心球硫化镉/镍钴磷异质结光催化剂的过程中,镍钴磷的用量为35mg,空心球硫化镉的用量为0.5g,本实施例制备的空心球硫化镉/镍钴磷异质结光催化剂标记为HCS/NCP7。
实施例3
本实施例空心球硫化镉/镍钴磷异质结光催化剂的制备步骤与实施例1相同,但本实施例制备空心球硫化镉/镍钴磷异质结光催化剂的过程中,镍钴磷的用量为45mg,空心球硫化镉的用量为0.5g,本实施例制备的空心球硫化镉/镍钴磷异质结光催化剂标记为HCS/NCP8。
对比例1
称取50mg的SiO2超声分散于75mL去离子水中,SiO2为直径200nm的纳米球,超声20min后得混合液A,然后称取1.067g Cd(CH3COO)2·2H2O和1.140g CH4N2加入到混合液A中,搅拌30min得到混合液B;之后将混合液B转移至100mL带不锈钢外壳的聚四氟乙烯反应釜中,在180℃下反应18h,反应结束,待反应釜自然冷却至室温后,取出反应后的固体样品并用去离子水和乙醇离心洗涤,离心产物在60℃下干燥,制得实心硫化镉纳米颗粒,标记为CS。
对比例2
在室温条件下,精确称取50mg的SiO2超声分散于75mL去离子水中,SiO2为直径200nm的纳米球,超声20min后得混合液A,然后称取1.067g Cd(CH3COO)2·2H2O和1.140gCH4N2加入到混合液A中,搅拌30min得到混合液B;之后将混合液B转移至100mL带不锈钢外壳的聚四氟乙烯反应釜中,在180℃下反应18h,反应结束,待反应釜自然冷却至室温后,取出反应后的固体样品并用去离子水和乙醇离心洗涤,离心产物在60℃下干燥,制得固体A;将固体A加入到100g/mLNaOH溶液当中,于90℃恒温水浴并搅拌3h,反应结束后,将所得固体样品用去离子水和乙醇离心洗涤,烘干后得到空心球硫化镉,标记为HCS。
应用例
对实施例1~3中所制得的空心球硫化镉/镍钴磷异质结光催化剂,以及对比例1所得的实心硫化镉纳米球,对比例2所得的空心球硫化镉进行光催化分解水产氢活性评价,具体操作步骤为:
取8.4gNa2S、3.15gNa2SO3和20mg催化剂置于反应器中,然后加100mL去离子水,超声5min。将反应器安装在装置上并用6℃的循环冷却水冷却,整个系统用真空泵抽至真空。活性测试采用300W氙灯作为光源进行产氢实验测试,氙灯工作电流为15A,反应共进行4h,每隔1h取一次样,并用带TCD检测器的气相色谱仪对所产生的氢气进行分析。
实施例1~3、对比例1~2的光催化分解水产氢速率如图1所示,可以看到所有实施例的光催化分解水产氢活性均高于对比例,且HCS/NCP7产氢速率为13.47mmol/(h·g),是HSC的4倍,是CS的13.6倍。
空心球硫化镉/镍钴磷异质结光催化剂的表征
1、XRD分析
图2为实施例1~3、对比例1~2的XRD图谱,与标准卡片(CdS JCPDS 65-3414,NiCoP JCPDS 71-2336)对比可知,实施例均存在CdS和NiCoP两种物质,结晶良好,且不存在其他杂相,同时随着NiCoP加入量的增加,NiCoP的衍射峰逐渐增强;对比例1和对比例2均为纯的CdS。
2、SEM分析
图3为对比例1、2的扫描电子显微镜图,可以看出CS和HCS为均匀分散的纳米球。其中,CS呈现直径为400-500nm的实心纳米球结构,HCS呈现直径为700nm、厚度为170nm的空心纳米球结构。
3、光致发光光谱分析
图4为实施例2、对比例1~2的光致发光光谱,可以看到HCS/NCP7的光谱强度最低,表明其光生载流子的传输和分离效率更高,因此促进了光催化分解水产氢活性。
尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法,其特征在于,制备步骤如下:
S1.将SiO2分散到去离子水中,再加入Cd(CH3COO)2·2H2O、CH4N2S(硫脲)进行搅拌,形成混合溶液;
S2.将混合溶液转移到100mL带不锈钢外壳的聚四氟乙烯反应釜中,进行水热反应,反应结束后自然冷却至室温;
S3.用去离子水和无水乙醇对步骤S2水热反应后的固体物质进行洗涤,再烘干;
S4.将步骤S3烘干后的固体物质放入热碱液中,充分反应后,取出固体产物,并用去离子水和无水乙醇洗涤,烘干后制得空心球硫化镉;
S5.取适量NiCl2·6H2O、CoCl2·6H2O和NaH2PO2·H2O放入研钵中研磨,研磨后焙烧,即得镍钴磷;
S6.取适量步骤S4制得的空心球硫化镉与步骤S5制得的镍钴磷分散到无水乙醇中,再超声、搅拌;
S7.将步骤S6超声搅拌后的固体产物烘干,即得空心球硫化镉/镍钴磷异质结光催化剂。
2.根据权利要求1所述的一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法,其特征在于:所述步骤S1中,SiO2为直径200~500nm的纳米球结构,使用量为5~100mg;Cd(CH3COO)2·2H2O与CH4N2S的摩尔比为1:(1~4)。
3.根据权利要求1所述的一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法,其特征在于:所述步骤S4中,热碱液为50~500g/L的NaOH溶液,反应温度为90℃,反应时间为3h。
4.根据权利要求1所述的一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法,其特征在于:所述步骤S5中,所述NiCl2·6H2O、CoCl2·6H2O、NaH2PO2·H2O的摩尔比为0.7:0.3:3。
5.根据权利要求1所述的一种空心球硫化镉/镍钴磷异质结光催化剂的制备方法,其特征在于:所述步骤S6中,镍钴磷与空心球硫化镉的质量比为(1~20):100。
6.一种空心球硫化镉/镍钴磷异质结光催化剂的应用,其特征在于:将根据权利要求1~5任意一项所述制备方法制备的空心球硫化镉/镍钴磷异质结光催化剂应用于光催化分解水。
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