CN108404921A - 一种B位过剩的Ruddlesden-Popper纳米催化材料 - Google Patents
一种B位过剩的Ruddlesden-Popper纳米催化材料 Download PDFInfo
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- 238000006555 catalytic reaction Methods 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
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- 229910021645 metal ion Inorganic materials 0.000 claims description 4
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
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- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010586 diagram Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
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- 230000017105 transposition Effects 0.000 description 5
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- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical class [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 4
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
本发明属于催化材料技术领域,公开了一种B位过剩的Ruddlesden‑Popper纳米催化材料。所述催化材料的化学表达式为A2B1+xO4,其中x=0~0.05,A位为镧系金属,B位为金属镍。将镧系金属化合物、镍源化合物按2:(1+x)的比例溶于蒸馏水或硝酸中,加入络合剂,调节pH值至6~9,120~200℃下加热搅拌蒸干,然后依次于300~450℃煅烧、900~1200℃烧结成相,得到前驱粉体;将前驱粉体在醇类溶剂下球磨处理,然后加入分散剂,离心,固体沉淀物于500~800℃煅烧去除有机残留物,得到产物。
Description
技术领域
本发明属于催化材料技术领域,具体涉及一种B位过剩的Ruddlesden-Popper纳米催化材料。
背景技术
催化剂对于处理最紧迫的社会和环境的挑战至关重要,无论是从化石燃料有害性气体及温室气体的减排,到可持续的清洁能源和化学品的生产,都离不开催化剂。催化剂将化石燃料燃烧排放的有害性气体转化为良性分子H2O和N2。而CO2的减排则需要开发先进的储能设备和捕捉CO2的技术,进而逐步以太阳能等可持续能源应用取代化石燃料。其中,当今太阳能设备的白昼和夜晚所存在的能源供应间歇问题,通过材料的电化学储能可以得到有效的解决。尽管锂离子电池已经在运输工具和一些固定的设备中得到广泛应用,但更高活性单位质量和单位体积的材料依然具有广泛的工业运用前景。
不幸的是,由于主反应的动力学反应缓慢,这些已被应用的设备的效率普遍较低。提高生产清洁气体和可持续能源的效率需要具有地球丰富的元素构成和较比现今更好活性和稳定性的催化剂。一方面贵金属催化剂在处理空气污染物和燃料电池氧还原方面得到很好的开发应用;另一方面具有高活性、选择性和稳定性的无机非贵金属材料也很好的迎合了全球环境和能源需求。
Ruddlesden-Popper材料具有组成结构可调节的特点,但通过材料的选取以及制备方法制备出性能更加优异的催化剂,仍是本领域技术人员需要解决的技术问题。
发明内容
针对以上现有技术存在的缺点和不足之处,本发明的首要目的在于提供一种B位过剩的Ruddlesden-Popper纳米催化材料。
本发明的另一目的在于提供上述B位过剩的Ruddlesden-Popper纳米催化材料的制备方法。
本发明目的通过以下技术方案实现:
一种B位过剩的Ruddlesden-Popper纳米催化材料,其化学表达式为A2B1+xO4,其中x=0~0.05,A位为镧系金属,B位为金属镍。
优选地,所述A位为镧、铈、镨或钕。
上述B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,包括如下制备步骤:
(1)将镧系金属化合物、镍源化合物按金属离子摩尔比A:Ni=2:(1+x)的比例溶于蒸馏水或硝酸中,加入络合剂混合搅拌,调节pH值至6~9,120~200℃下加热搅拌蒸干,然后于300~450℃煅烧,再于900~1200℃烧结成相,得到前驱粉体;
(2)将所得前驱粉体在醇类溶剂条件下球磨处理、过筛分离,得到混合液;
(3)往所得混合液中加入分散剂,离心处理,固体沉淀物于500~800℃煅烧去除有机残留物,得到所述B位过剩的Ruddlesden-Popper纳米催化材料。
优选地,所述镧系金属化合物为镧源、铈源、镨源或钕源;所述镧源选自硝酸镧、乙酸镧、草酸镧或氧化镧;所述铈源选自硝酸铈、乙酸铈、草酸铈或二氧化铈;所述镨源选自硝酸镨、乙酸镨或氧化镨;所述钕源选自硝酸钕、乙酸钕或氧化钕。
优选地,所述镍源化合物选自硝酸镍或乙酸镍。
优选地,所述络合剂选自乙二胺四乙酸、柠檬酸和甘氨酸中的至少一种;所述络合剂与金属离子的总摩尔数之比为(2~4):1。
优选地,所述的醇类溶剂选自乙醇或异丙醇。
优选地,所述的球磨处理所使用的球磨珠的材质为氧化锆珠、硅酸锆珠、锆铝复合珠或陶瓷微珠,球磨珠的直径为0.2~10mm。
优选地,所述分散剂选自聚乙烯醇、聚乙二醇、柠檬酸铵、甲基戊醇、聚丙烯酰胺、纤维素衍生物中的至少一种;分散剂的加入量与混合液的体积比为1:(3~5)。
优选地,所述离心处理的转速为1000~6000r/min。
本发明的制备方法及所得到的产物具有如下优点及有益效果:
(1)本发明选取的镧系和镍源化合物都为非贵金属化合物,大大节约了催化剂制备的成本;
(2)本发明采用球磨和离心的方法,所制备的催化剂材料具有均一的粒径分布,优化的微观尺寸产生出更加优异的催化性能;
(3)本发明选取B位过剩的Ruddlesden-Popper催化材料,相较无过剩的结构,在催化活性上也有明显提高。
附图说明
图1为实施例1~3所得催化材料P2NO、P2N1.025O、P2N1.05O的XRD图。
图2为实施例4~6所得催化材料N2NO、N2N1.025O、N2N1.05O的XRD图。
图3为实施例1所得催化材料P2NO的SEM图。
图4为实施例1所得催化材料P2NO的Malvern图。
图5为实施例1所得催化材料P2NO与比较例所得催化材料BJ-P2NO的氧还原(ORR)性能测试结果图。
图6为实施例1~3所得催化材料P2NO、P2N1.025O、P2N1.05O的氧还原(ORR)性能测试结果图。
图7为实施例4~6所得催化材料N2NO、N2N1.025O、N2N1.05O的氧还原(ORR)性能测试结果图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
比较例
将0.2mol硝酸镨、0.1mol硝酸镍溶于蒸馏水中,加入0.6mol的柠檬酸与0.3mol的乙二胺四乙酸混合搅拌,滴加氨水调节pH为8,150℃下加热搅拌蒸干成凝胶,转置电炉300℃下燃烧释放有机元素C、N、H,再在马弗炉中1200℃烧12小时成相,用研钵磨细得到粉体BJ-P2NO。
实施例1
(1)将0.2mol硝酸镨、0.1mol硝酸镍溶于蒸馏水中,加入0.6mol的柠檬酸与0.3mol的乙二胺四乙酸混合搅拌,滴加氨水调节pH为8,150℃下加热搅拌蒸干成凝胶,转置电炉300℃下燃烧释放有机元素C、N、H,再在马弗炉中1200℃烧12小时成相,得到前驱粉体。
(2)将10g步骤(1)所得前驱粉体配以0.3mm球磨珠100g,其中3.0mm球磨珠20个,10mm球磨珠5个,在球磨机上球磨24小时,溶剂使用乙醇。随后过筛,收集混合液。
(3)取30ml步骤(2)的混合液于离心管中,加入10ml聚乙二醇,2000r/min条件下离心处理,湿的粉体在600℃炉中煅烧5小时,烧去有机残留物,得到粉体P2NO。
本实施例所得催化材料P2NO的XRD图、SEM图和Malvern图分别如图1、图3和图4所示。
实施例2
(1)将0.2mol硝酸镨、0.1025mol硝酸镍溶于蒸馏水中,加入0.605mol的柠檬酸与0.3025mol的乙二胺四乙酸混合搅拌,滴加氨水调节pH为8,150℃下加热搅拌蒸干成凝胶,转置电炉300℃下燃烧释放有机元素C、N、H,再在马弗炉中1200℃烧12小时成相,得到前驱粉体。
(2)将10g步骤(1)所得前驱粉体配以0.3mm球磨珠100g,其中3.0mm球磨珠20个,10mm球磨珠5个,在球磨机上球磨24小时,溶剂使用乙醇。随后过筛,收集混合液。
(3)取30ml步骤(2)的混合液于离心管中,加入10ml聚乙二醇,2000r/min条件下离心处理,湿的粉体在600℃炉中煅烧5小时,烧去有机残留物,得到粉体P2N1.025O。
本实施例所得催化材料P2N1.025O的XRD图如图1所示。
实施例3
(1)将0.2mol硝酸镨、0.105mol硝酸镍溶于蒸馏水中,加入0.61mol的柠檬酸与0.305mol的乙二胺四乙酸混合搅拌,滴加氨水调节pH为8,150℃下加热搅拌蒸干成凝胶,转置电炉300℃下燃烧释放有机元素C、N、H,再在马弗炉中1200℃烧12小时成相,得到前驱粉体。
(2)将10g步骤(1)所得前驱粉体配以0.3mm球磨珠100g,其中3.0mm球磨珠20个,10mm球磨珠5个,在球磨机上球磨24小时,溶剂使用乙醇。随后过筛,收集混合液。
(3)取30ml步骤(2)的混合液于离心管中,加入10ml聚乙二醇,2000r/min条件下离心处理,湿的粉体在600℃炉中煅烧5小时,烧去有机残留物,得到粉体P2N1.05O。
本实施例所得催化材料P2N1.05O的XRD图如图1所示。
实施例4
(1)将0.2mol硝酸钕、0.1mol硝酸镍溶于蒸馏水中,加入0.6mol的柠檬酸与0.3mol的乙二胺四乙酸混合搅拌,滴加氨水调节pH为8,150℃下加热搅拌蒸干成凝胶,转置电炉300℃下燃烧释放有机元素C、N、H,再在马弗炉中1200℃烧12小时成相,得到前驱粉体。
(2)将10g步骤(1)所得前驱粉体配以0.3mm球磨珠100g,其中3.0mm球磨珠20个,10mm球磨珠5个,在球磨机上球磨24小时,溶剂使用乙醇。随后过筛,收集混合液。
(3)取30ml步骤(2)的混合液于离心管中,加入10ml聚乙二醇,2000r/min条件下离心处理,湿的粉体在600℃炉中煅烧5小时,烧去有机残留物,得到粉体N2NO。
本实施例所得催化材料N2NO的XRD图如图2所示。
实施例5
(1)将0.2mol硝酸钕、0.1025mol硝酸镍溶于蒸馏水中,加入0.605mol的柠檬酸与0.3025mol的乙二胺四乙酸混合搅拌,滴加氨水调节pH为8,150℃下加热搅拌蒸干成凝胶,转置电炉300℃下燃烧释放有机元素C、N、H,再在马弗炉中1200℃烧12小时成相,得到前驱粉体。
(2)将10g步骤(1)所得前驱粉体配以0.3mm球磨珠100g,其中3.0mm球磨珠20个,10mm球磨珠5个,在球磨机上球磨24小时,溶剂使用乙醇。随后过筛,收集混合液。
(3)取30ml步骤(2)的混合液于离心管中,加入10ml聚乙二醇,2000r/min条件下离心处理,湿的粉体在600℃炉中煅烧5小时,烧去有机残留物,得到粉体N2N1.025O。
本实施例所得催化材料N2N1.025O的XRD图如图2所示。
实施例6
(1)将0.2mol硝酸钕、0.105mol硝酸镍溶于蒸馏水中,加入0.61mol的柠檬酸与0.305mol的乙二胺四乙酸混合搅拌,滴加氨水调节pH为8,150℃下加热搅拌蒸干成凝胶,转置电炉300℃下燃烧释放有机元素C、N、H,再在马弗炉中1200℃烧12小时成相,得到前驱粉体。
(2)将10g步骤(1)所得前驱粉体配以0.3mm球磨珠100g,其中3.0mm球磨珠20个,10mm球磨珠5个,在球磨机上球磨24小时,溶剂使用乙醇。随后过筛,收集混合液。
(3)取30ml步骤(2)的混合液于离心管中,加入10ml聚乙二醇,2000r/min条件下离心处理,湿的粉体在600℃炉中煅烧5小时,烧去有机残留物,得到粉体N2N1.05O。
本实施例所得催化材料N2N1.05O的XRD图如图2所示。
以上比较例及实施例所得催化材料制备电极及电极氧还原(ORR)测试方法如下:
1)催化剂浆料制备:称取10mg待测试催化材料粉体分散在1mL的乙醇中,再向其中加入50μL的Nafion(质量分数5%)溶液,超声震荡1小时后得到均匀的催化剂浆料。
2)电极制备:将步骤1)制备的催化剂浆料用微量注射器取5μL滴于圆盘面积为0.19635cm2的旋转圆盘电极(RDE)上,自然风干。
3)电极活性的测试:将步骤2)所得电极装在旋转圆盘装置(Pine公司)上进行电化学测试,测试方法如下:
A)电极测试的体系要求为三电极体系(玻碳电极为工作电极,铂片或铂丝为对电极,饱和甘汞电极为参比电极),电解质选择0.1mol/L的KOH溶液。
B)在进行测试前,先向电解质溶液中持续通纯氧30分钟以上,通气流速为30~60mL/s,保证其中氧气的饱和,在测试过程中也不要停止通气。
C)测试氧还原(ORR)活性,进行极化曲线测试(LSV),电压扫描范围为-1~0.2V,扫速为5mV/s,转速设定为1600rpm。
经测试实施例1所得催化材料P2NO与比较例所得催化材料BJ-P2NO的氧还原(ORR)性能测试结果如图5所示。实施例1~3所得催化材料P2NO、P2N1.025O、P2N1.05O的氧还原(ORR)性能测试结果如图6所示。实施例4~6所得催化材料N2NO、N2N1.025O、N2N1.05O的氧还原(ORR)性能测试结果如图7所示。
由以上结果可以看出:BJ-P2NO、P2NO、P2N1.025O、P2N1.05O的起峰电位相同,但在极限电流密度对比上,P2NO的2.52mA/cm2是BJ-P2NO的2.29mA/cm2的1.10倍,而P2N1.025O的2.68mA/cm2是P2NO的1.06倍,P2N1.05O的2.91mA/cm2是P2NO的1.15倍。同样的,在N2NO、N2N1.025O、N2N1.05O的极限电流密度对比中,三者的起峰电位相同,N2NO的值为2.42mA/cm2,N2N1.025O的2.56mA/cm2是N2NO的1.06倍,N2N1.05O的2.71mA/cm2是N2NO的1.12倍。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种B位过剩的Ruddlesden-Popper纳米催化材料,其特征在于:所述催化材料的化学表达式为A2B1+xO4,其中x=0~0.05,A位为镧系金属,B位为金属镍。
2.根据权利要求1所述的一种B位过剩的Ruddlesden-Popper纳米催化材料,其特征在于:所述A位为镧、铈、镨或钕。
3.权利要求1或2所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于包括如下制备步骤:
(1)将镧系金属化合物、镍源化合物按金属离子摩尔比A:Ni=2:(1+x)的比例溶于蒸馏水或硝酸中,加入络合剂混合搅拌,调节pH值至6~9,120~200℃下加热搅拌蒸干,然后于300~450℃煅烧,再于900~1200℃烧结成相,得到前驱粉体;
(2)将所得前驱粉体在醇类溶剂条件下球磨处理、过筛分离,得到混合液;
(3)往所得混合液中加入分散剂,离心处理,固体沉淀物于500~800℃煅烧去除有机残留物,得到所述B位过剩的Ruddlesden-Popper纳米催化材料。
4.根据权利要求3所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于:所述镧系金属化合物为镧源、铈源、镨源或钕源;所述镧源选自硝酸镧、乙酸镧、草酸镧或氧化镧;所述铈源选自硝酸铈、乙酸铈、草酸铈或二氧化铈;所述镨源选自硝酸镨、乙酸镨或氧化镨;所述钕源选自硝酸钕、乙酸钕或氧化钕。
5.根据权利要求3所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于:所述镍源化合物选自硝酸镍或乙酸镍。
6.根据权利要求3所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于:所述络合剂选自乙二胺四乙酸、柠檬酸和甘氨酸中的至少一种;所述络合剂与金属离子的总摩尔数之比为(2~4):1。
7.根据权利要求3所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于:所述的醇类溶剂选自乙醇或异丙醇。
8.根据权利要求3所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于:所述的球磨处理所使用的球磨珠的材质为氧化锆珠、硅酸锆珠、锆铝复合珠或陶瓷微珠,球磨珠的直径为0.2~10mm。
9.根据权利要求3所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于:所述分散剂选自聚乙烯醇、聚乙二醇、柠檬酸铵、甲基戊醇、聚丙烯酰胺、纤维素衍生物中的至少一种;分散剂的加入量与混合液的体积比为1:(3~5)。
10.根据权利要求3所述的一种B位过剩的Ruddlesden-Popper纳米催化材料的制备方法,其特征在于:所述离心处理的转速为1000~6000r/min。
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