CN103949271B - 一种钴锰水滑石负载纳米金催化剂及其制备方法 - Google Patents
一种钴锰水滑石负载纳米金催化剂及其制备方法 Download PDFInfo
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Abstract
一种钴锰水滑石负载纳米金催化剂及其制备方法,属于电催化剂技术领域。催化剂的化学组成为:CoMn-LDHs/AuNPs,其中AuNPs为金纳米粒子,粒子大小7.2~13.8nm。CoMn-LDHs为钴锰水滑石。该催化剂的制备方法包括以下步骤:采用成核晶化隔离法制备碳酸根插层的钴锰水滑石,将其分散液滴涂到铟-锡金属氧化物ITO导电玻璃电极制备钴锰水滑石修饰导电玻璃电极,在含四氯金酸的磷酸盐缓冲溶液中,钴锰水滑石/ITO导电玻璃工作电极上进行电化学还原制备金纳米粒子。优点在于,所制备的钴锰水滑石负载纳米金催化剂,其金纳米粒子分布均匀,稳定性高,电催化氧化过氧化氢灵敏度高。
Description
技术领域
本发明属于电催化剂技术领域,具体涉及一种钴锰水滑石负载纳米金催化剂及其制备方法,制备组成为CoMn-LDHs/AuNPs催化剂。
背景技术
贵金属纳米材料由于催化效率高、选择性强,是备受人们青睐的固体催化剂,但是由于贵金属纳米材料在制备过程中容易团聚,分散性差、稳定性差导致其催化性能降低,在一定程度抑制了贵金属催化剂的发展。而发展载体制备负载型贵金属催化剂,是通过引入外来物种来稳定单分散的贵金属纳米粒子(NPs)。
层状双金属氢氧化物(Layereddoublehydroxide,简写LDHs,俗称水滑石)是经典的层状结构。其结构与水镁石结构类似,由层板和层间阴离子构成层状结构。由于其层板金属元素以原子水平高度均匀分散的结构特点,层状双金属氢氧化物及其前驱体煅烧产物作载体时具有独特的优势。目前已有报道的负载金的水滑石,其层板是由单一过渡金属元素与金属铝元素组成[参考:(a)B.Ballarin,A.Mignani,E.Scavetta,M.Giorgetti,D.Tonelli,E.Boanini,C.Mousty,V.Prevot.Langmuir.2012,28,15065-15074.(b)Y.L.Wang,D.D.Zhang,M.Tang,S.D.X,M.G.Li.Electrochim.Acta.,2010,55,4045-4049]。而双过渡金属元素组成的CoMn-LDHs在负载纳米金催化剂方面还未见报道。
发明内容
本发明目的在于提供一种钴锰水滑石负载纳米金催化剂及其制备方法,钴、锰双过渡金属组成的载体LDHs负载纳米金催化剂,是一种高稳定、高催化的催化剂。
本发明的钴锰水滑石负载纳米金催化剂的化学组成为:CoMn-LDHs/AuNPs,其中AuNPs为金纳米粒子,粒子大小7.2~13.8nm。CoMn-LDHs为钴锰水滑石,所述的钴锰水滑石的化学式是:[Co1-xMnx(OH)2]x+(CO3 2-)x/2·mH2O,其中0.2≤x≤0.33,m为结晶水数目,取值范围为0.5~9。
本发明的钴锰水滑石负载纳米金催化剂的制备方法的工艺步骤如下:
(1)取CoMn-LDHs粉末分散于2:1~5:1(v/v)的异丙醇:水混合溶液中,使其保持浓度在1~5mg/mL范围内,超声分散2~5小时,制得CoMn-LDHs分散液;
(2)取CoMn-LDHs分散液滴涂于铟-锡金属氧化物(ITO)导电玻璃电极,每平方厘米的滴涂量为10~30μL,在20~25℃晾干,制得CoMn-LDHs修饰ITO导电玻璃电极;
(3)将CoMn-LDHs/ITO导电玻璃电极置于含0.1~1mM四氯金酸的磷酸盐缓冲溶液pH6.0~8.0,在N2氛围下-0.9~+0.1V电压范围内扫描10~20圈,扫速20~50mV/s,得到CoMn-LDHs/AuNPs。
所述的钴锰水滑石的制备步骤为:
采用成核晶化隔离法制备钴锰水滑石。将Co2+的硝酸盐和Mn2+的硝酸盐(49%~51%)按摩尔配比[Co2+]/[Mn2+]=2~4,用去离子水配成100mL~200mL盐溶液,金属离子总浓度[Co2+]+[Mn2+]=0.02~0.2mol/L,另将NaOH和Na2CO3,[OH-]/([Co2+]+[Mn2+])=1~3,[CO3 2-]/[Mn2+]=1~3,用去离子水配成100~200mL碱溶液,将两种溶液同时倒入全返混反应器中,反应1~2min,取出浆液在20~50℃搅拌条件下晶化5~10小时,晶化结束后,反应液离心洗涤至pH为7.0~7.5,放入干燥箱中50℃~100℃干燥12~24小时,得到CoMn-LDHs。
本发明的优点:所制备的钴锰水滑石负载纳米金催化剂,其金纳米粒子分布均匀,稳定性高,电催化氧化过氧化氢的灵敏度高。
附图说明
图1是本发明实施例1得到的Co3Mn-LDHs(a)、Co3Mn-LDHs/AuNPs(b)的X射线衍射(XRD)表征图。由a可知,出现了钴锰水滑石的特征衍射峰,证明钴锰水滑石成功制备。由b可知,出现了金纳米粒子的特征衍射峰,证明纳米金生成。
图2是实施例1得到的Co3Mn-LDHs/AuNPs的扫描电镜(SEM)表征图。SEM表征表明AuNPs均匀分布。
图3是实施例1得到的Co3Mn-LDHs/AuNPs的循环伏安图(CVs)表征图,测试底液为100mMPBS(pH7.0)溶液。在+0.45V和+0.96V的一对氧化还原峰归属于金纳米粒子的氧化还原峰。经过50圈的扫描后,其还原峰电流保留起始的97.3%。
图4是实施例1得到的Co3Mn-LDHs/AuNPs在电位为+0.55V时,对H2O2的计时安培响应图。
图5是实施例1得到的Co3Mn-LDHs/AuNPs在100mMPBS(pH7.0)中H2O2的浓度与响应电流的线性关系曲线图,其线性范围1.00×10-7~1.02×10-3M,灵敏度为129.5μA/(mM·cm2)。
具体实施方式
本发明中采用日本岛津XRD-6000型X射线衍射仪对制备的产物进行结构分析,采用ZeissSupra55场发射电镜进行样品形貌分析,采用上海辰华公司的CHI660C进行催化剂材料稳定性及电催化过氧化氢性能分析。电化学沉积和电化学测试采用三电极体系,Ag/AgCl为参比电极,Pt片为对电极,钴锰水滑石/金纳米粒子修饰的铟-锡金属氧化物导电玻璃(ITO)电极为工作电极。
实施例1:
1.载体Co3Mn-LDHs的制备
采用成核晶化隔离法制备3:1钴锰水滑石,称取4.3658gCo(NO3)2·6H2O和1.7895gMn(NO3)2(49%~51%)溶解在100mL去离子水中,配成混合盐溶液,称取1.28gNaOH和1.06gNa2CO3溶解在100mL去离子水,配成混合碱溶液。将两种混合溶液同时加入全返混液膜反应器,反应2min,将得到的混合浆液转移到三口烧瓶中恒温剧烈搅拌,30℃晶化5小时后取出浆液,用去离子水清洗至pH为7,于50℃干燥12小时,得到Co3Mn-LDHs。
2.Co3Mn-LDHs/AuNPs催化剂制备
取1mgCo3Mn-LDHs粉末分散于1mL2:1(v/v)的异丙醇:水混合溶液中,超声分散2小时,制得1mg/mLCo3Mn-LDHs分散液。取Co3Mn-LDHs分散液滴涂铟-锡金属氧化物(ITO)导电玻璃电极,每平方厘米的滴涂量为20μL。室温25℃晾干,制得Co3Mn-LDHs修饰ITO导电玻璃电极。将Co3Mn-LDHs/ITO导电玻璃电极置于含0.2mM四氯金酸的磷酸盐缓冲溶液(pH7.0),在N2氛围下-0.9~+0.1电位范围内扫描20圈,扫速50mV/s,得到Co3Mn-LDHs/AuNPs。
3.Co3Mn-LDHs/AuNPs催化剂材料稳定性和电催化过氧化氢性能评价
经过50圈循环扫描后,Co3Mn-LDHs/AuNPs催化剂保留起始还原峰电流的97.3%。在100mMPBS(pH7.0)溶液中,电位+0.55V下检测H2O2的灵敏度为129.5μA/(mM·cm2)。
实施例2:
1.载体Co2Mn-LDHs的制备
采用成核晶化隔离法制备2:1钴锰水滑石,称取38.809gCo(NO3)2·6H2O和23.86gMn(NO3)2(49%~51%)溶解在200mL去离子水中,配成混合盐溶液,称取8gNaOH和21.2gNa2CO3溶解在200mL去离子水,配成混合碱溶液。将两种混合溶液同时加入全返混液膜反应器,反应1min,将得到的混合浆液转移到三口烧瓶中恒温剧烈搅拌,20℃晶化10小时后取出浆液,用去离子水清洗至pH为7.1,于100℃干燥24小时,得到Co2Mn-LDHs。
2.Co2Mn-LDHs/AuNPs催化剂的制备
取2mgCo2Mn-LDHs粉末分散于1mL3:1(v/v)的异丙醇:水混合溶液中,超声分散3小时,制得2mg/mLCo2Mn-LDHs分散液。取Co2Mn-LDHs分散液滴涂于铟-锡金属氧化物(ITO)导电玻璃电极,每平方厘米滴涂量为10μL。室温20℃晾干,制得Co2Mn-LDHs修饰ITO导电玻璃电极。将Co2Mn-LDHs/ITO导电玻璃电极置于含0.1mM四氯金酸的磷酸盐缓冲溶液(pH6.0),在N2氛围下-0.9~+0.1V电压范围内扫描10圈,扫速20mV/s,得到Co2Mn-LDHs/AuNPs。
3.Co2Mn-LDHs/AuNPs催化剂材料稳定性和电催化过氧化氢性能评价
经过50圈循环扫描后,Co2Mn-LDHs/AuNPs催化剂保留起始还原峰电流的96.8%。在100mMPBS(pH7.0)溶液中,电位+0.55V下检测H2O2的灵敏度为123.6μA/(mM·cm2)。
实施例3:
1.载体Co4Mn-LDHs的制备
采用成核晶化隔离法制备4:1钴锰水滑石,称取23.2824gCo(NO3)2·6H2O和3.579gMn(NO3)2(49%~51%)溶解在200mL去离子水中,配成混合盐溶液,称取12gNaOH和2.12gNa2CO3溶解在200mL去离子水,配成混合碱溶液。将两种混合溶液同时加入全返混液膜反应器,反应2min,将得到的混合浆液转移到三口烧瓶中恒温剧烈搅拌,50℃晶化6小时后取出浆液,用去离子水清洗至上清液pH为7.5,于60℃干燥18小时,得到Co4Mn-LDHs。
2.Co4Mn-LDHs/AuNPs催化剂的制备
取6mgCo4Mn-LDHs粉末分散于2mL4:1(v/v)的异丙醇:水混合溶液中,超声分散4小时,制得3mg/mLCo4Mn-LDHs分散液。取Co4Mn-LDHs分散液滴涂于铟-锡金属氧化物(ITO)导电玻璃电极,每平方厘米滴涂量为30μL。室温21℃晾干,制得Co4Mn-LDHs修饰ITO导电玻璃电极。将Co4Mn-LDHs/ITO导电玻璃电极置于含1mM四氯金酸的磷酸盐缓冲溶液(pH8.0),在N2氛围下-0.9~+0.1V电压范围内扫描12圈,扫速25mV/s,得到Co4Mn-LDHs/AuNPs。
3.Co4Mn-LDHs/AuNPs催化剂材料稳定性和电催化过氧化氢性能评价
经过50圈循环扫描后,Co4Mn-LDHs/AuNPs保留起始还原峰电流的96.8%。在100mMPBS(pH7.0)溶液中,电位+0.55V下检测H2O2的灵敏度为125.3μA/(mM·cm2)。
实施例4:
1.载体Co3Mn-LDHs的制备
采用成核晶化隔离法制备3:1钴锰水滑石,称取4.3658gCo(NO3)2·6H2O和1.7895gMn(NO3)2(49%~51%)溶解在150mL去离子水中,配成混合盐溶液,称取1.28gNaOH和1.06gNa2CO3溶解在150mL去离子水,配成混合碱溶液。将两种混合溶液同时加入全返混液膜反应器,反应1min,将得到的混合浆液转移到三口烧瓶中恒温剧烈搅拌,40℃晶化7小时后取出浆液,用去离子水清洗至pH为7.2,于70℃干燥12小时,得到Co3Mn-LDHs。
2.Co3Mn-LDHs/AuNPs催化剂的制备
取4mgCo3Mn-LDHs粉末分散于1mL5:1(v/v)的异丙醇:水混合溶液中,超声分散2.5小时,制得4mg/mLCo3Mn-LDHs分散液。取Co3Mn-LDHs分散液滴涂于铟-锡金属氧化物(ITO)导电玻璃电极,每平方厘米滴涂量为15μL。室温22℃晾干,制得Co3Mn-LDHs修饰ITO导电玻璃电极。将Co3Mn-LDHs/ITO导电玻璃电极置于含0.5mM四氯金酸的磷酸盐缓冲溶液(pH7.5),在N2氛围下-0.9~0.1V电压范围内扫描16圈,扫速35mV/s,得到Co3Mn-LDHs/AuNPs。
3.Co3Mn-LDHs/AuNPs催化剂材料稳定性和电催化过氧化氢性能评价
经过50圈循环扫描后,Co3Mn-LDHs/AuNPs保留起始还原峰电流的95.8%。在100mMPBS(pH7.0)溶液中,电位+0.55V下检测H2O2的灵敏度为127.8μA/(mM·cm2)。
实施例5:
1.载体Co3Mn-LDHs的制备
采用成核晶化隔离法制备3:1钴锰水滑石,称取4.3658gCo(NO3)2·6H2O和1.7895gMn(NO3)2(49%~51%)溶解在100mL去离子水中,配成混合盐溶液,称取1.28gNaOH和1.06gNa2CO3溶解在100mL去离子水,配成混合碱溶液。将两种混合溶液同时加入全返混液膜反应器,反应2min,将得到的混合浆液转移到三口烧瓶中恒温剧烈搅拌,35℃晶化8小时后取出浆液,用去离子水清洗至上清液pH为7.4,于80℃干燥20小时,得到载体Co3Mn-LDHs。
2.AuNPs/Co3Mn-LDHs催化剂的制备
取5mgCo3Mn-LDHs粉末分散于1mL3:1(v/v)的异丙醇:水混合溶液中,超声分散5小时,制得5mg/mLCo3Mn-LDHs分散液。取Co3Mn-LDHs分散液滴涂于铟-锡金属氧化物(ITO)导电玻璃电极,每平方厘米滴涂量25μL。室温24℃晾干,制得Co3Mn-LDHs修饰ITO导电玻璃电极。将Co3Mn-LDHs/ITO导电玻璃电极置于含0.8mM四氯金酸的磷酸盐缓冲溶液(pH6.5),在N2氛围下-0.9~0.1V电压范围内扫描14圈,扫速45mV/s,得到Co3Mn-LDHs/AuNPs。
3.Co3Mn-LDHs/AuNPs催化剂材料稳定性和电催化过氧化氢性能评价
经过50圈循环扫描后,Co3Mn-LDHs/AuNPs保留起始还原峰电流的94.5%。在100mMPBS(pH7.0)溶液中,电位+0.55V下检测H2O2的灵敏度为126.9μA/(mM·cm2)。
Claims (3)
1.一种钴锰水滑石负载纳米金催化剂,其特征在于:化学组成为:CoMn-LDHs/AuNPs,其中AuNPs为金纳米粒子,粒子大小7.2~13.8nm;CoMn-LDHs为钴锰水滑石,所述的钴锰水滑石的化学式是:[Co1-xMnx(OH)2]x+(CO3 2-)x/2·mH2O,其中0.2≤x≤0.33,m为结晶水数目,取值范围为0.5~9。
2.一种权利要求1所述的催化剂的制备方法,其特征在于:工艺步骤如下:
(1)取CoMn-LDHs粉末分散于体积比为2:1~5:1的异丙醇:水混合溶液中,使其保持浓度在1~5mg/mL范围内,超声分散2~5小时,制得CoMn-LDHs分散液;
(2)取CoMn-LDHs分散液滴涂于铟-锡金属氧化物ITO导电玻璃电极,每平方厘米的滴涂量为10~30μL,在20~25℃晾干,制得CoMn-LDHs修饰ITO导电玻璃电极;
(3)将CoMn-LDHs/ITO导电玻璃电极置于含0.1~1mM四氯金酸的磷酸盐缓冲溶液pH6.0~8.0,在N2氛围下-0.9~+0.1V电压范围内扫描10~20圈,扫速20~50mV/s,得到CoMn-LDHs/AuNPs。
3.根据权利要求书2所述的制备方法,其特征在于:所述的钴锰水滑石的制备步骤为:
采用成核晶化隔离法制备钴锰水滑石:将Co2+的硝酸盐和纯度为49%~51%的Mn2+的硝酸盐按摩尔配比[Co2+]/[Mn2+]=2~4,用去离子水配成100mL~200mL盐溶液,金属离子总浓度[Co2+]+[Mn2+]=0.02~0.2mol/L,另将NaOH和Na2CO3,[OH-]/([Co2+]+[Mn2+])=1~3,[CO3 2-]/[Mn2+]=1~3,用去离子水配成100~200mL碱溶液,将两种溶液同时倒入全返混反应器中,反应1~2min,取出浆液在20~50℃搅拌条件下晶化5~10小时,晶化结束后,反应液离心洗涤至pH为7.0~7.5,放入干燥箱中50℃~100℃干燥12~24小时,得到CoMn-LDHs。
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