CN108070874B - 一种原子分散的水氧化催化剂及其制备和应用 - Google Patents
一种原子分散的水氧化催化剂及其制备和应用 Download PDFInfo
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- CN108070874B CN108070874B CN201611006770.2A CN201611006770A CN108070874B CN 108070874 B CN108070874 B CN 108070874B CN 201611006770 A CN201611006770 A CN 201611006770A CN 108070874 B CN108070874 B CN 108070874B
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Classifications
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
本发明涉及一种原子分散的水氧化催化剂及其制备方法和应用。该方法先将金属离子及非金属原子嵌入碳基材料骨架当中,通过酸处理除去生成的氧化物得到原子分散的催化剂。该方法可以制备含钒、铬、锰、铁、钴、镍、铜、钌、钯、银、镉、铱和铅等金属离子原子分散的催化剂。该方法合成的材料里面金属离子主要是以单原子的方式镶嵌在碳基载体的骨架中,且金属负载量可以高达1.5wt.%以上。该法制备的原子分散的催化材料在水氧化反应中的催化性能可以和自然界的PSII相媲美,且制备成本低廉,可以在电催化分解水、光电催化分解水和光催化分解水以及人工光合二氧化碳还原转化过程中,具有广阔的应用前景。
Description
技术领域
本发明涉及一种原子分散的水氧化催化剂,具体地说是一种用于水氧化的原子级锰分散的催化剂。本发明还涉及钒、铬、铁、钴、镍、铜、钌、钯、银、镉、铱、铅和氮等原子级分散的催化剂及其在水氧化中的应用。这些原子分散的催化剂可以应用电催化分解水、光电催化分解水和光催化分解水过程中。
背景技术
模拟绿色植物的光合作用,利用太阳光将H2O和CO2转化为O2和碳水化合物,不仅可以解决人类所面临的日益严峻的能源危机,而且还可以改善由于使用化石燃料所引起的环境问题。不管是光解水还是光还原二氧化碳,水的氧化是其中的重要步驟。然而由于水的氧化无论是从热力学角度还是动力学角度,均存在着非常大的挑战,复杂的水氧化过程一直制约着人工光合作用的发展。合成高效稳定的水氧化催化剂是突破水分解的关键。目前己报道的高效水氧化催化剂多数是基于贵金属钌和铱的金属有机配合物。由于其价格昂贵,且不稳定等因素从而制约它们的实际应用。由于第一过渡系金属原子不仅具有丰富的氧化还原态,且相对于其它过渡系金属在地球上更丰富的分布和更低的开采提炼成本,具有贵金属钌和铱不可比拟的重大优势和广阔的应用前景,因此最近几年来第一过渡系金属元素,尤其以锰、铁、钴为中心原子的水氧化催化剂得到了越来越多的重视。
Shannon S.Stahl等考察了不同氧化锰(α-MnO2,β-MnO2,R-MnO2,γ-MnO2,λ-MnO2,δ-MnO2,Mn2O3,Mn3O4)电化学水氧化性能(J.Am.Chem.Soc.2015,137,8384)。然而,该文章中氧化锰为体相材料,催化水氧化性能很低(TOF在10-5s-1数量级)。Brimblecombe等研究了一种四核锰氧簇催化剂在水氧化反应中的应用(PCT application WO 2008/116254)。但其催化水氧化性能还是太低,其水氧化TOF基本上还是处于10-3~10-5s-1之间。Heinz Frei等报道纳米级四氧化三钴负载在SBA-15中孔分子筛上(Angew.Chem.Int.Ed.2009,48,1841)和纳米级氧化锰负载在KIT-6中孔分子筛上(Chem.Commun.,2010,46,2920)。然而这些催化剂在水氧化反应中活性很低,其水氧化TOF基本上还是处于10-3~10-5s-1之间,离自然界的PSII(TOF为100-400s-1)差距太大。孙立成等报道一种钌基化合物[Ru(bda)(isoq)2]在化学水氧化反应中展示较高的催化性能(Nature Chemistry,2012,4,418)。其催化活性很高,但是稳定性差,只有几秒钟的稳定性,不适合实际应用。本专利制备的原子级锰基催化剂在水氧化反应中催化活性可以达到PSII的水平,TOF高达200s-1以上,且反应稳定性在100个小时以上,适宜实际应用。原子分散的催化剂具有高活性、高选择性和高稳定性(耐酸、耐碱及抗中毒能力强)等优点,是未来多相催化研究的一个热点。
发明内容
本发明的目的是提供一种原子分散的水氧化催化剂及其制备方法和应用。该方法先将金属离子及非金属原子嵌入碳基材料骨架当中,通过酸处理除去生成的氧化物得到原子分散的催化剂。
本发明采用的技术方案为:
一种原子分散的水氧化催化剂:于碳基载体的骨架中分散单原子形式的金属离子及非金属原子(如氮),且金属离子、碳原子及氮原子形成稳定的配位键。
金属离子、碳原子及氮原子形成稳定的配位键具体是金属与碳成键、金属与氮成键、碳与氮成键。
所述原子分散的水氧化催化剂中金属含量为0.01~2.0wt.%,氮含量为1-8wt.%。
所述碳基载体选自石墨片、氧化石墨烯、石墨烯、无定型碳、碳纳米管或多孔碳中的一种或二种以上。
金属为钒、铬、锰、铁、钴、镍、铜、钌、钯、银、镉、铱或铅中的一种或几种。
上述水氧化催化剂的制备方法:
1)将金属盐与碳基载体在水或有机溶剂中混合均匀,得到混合物1;
2)再用过滤、离心、冷冻干燥、旋转蒸发或加热蒸发中的一种或几种方法除去混合物1中的水或有机溶剂,得到混合物2;
3)对混合物2进行研磨,之后高温焙烧处理,得到固体粉末;
4)对固体粉末进行酸处理除去生成的氧化物,再过滤、洗涤、干燥,得到原子分散的水氧化催化剂。
所述金属盐中金属离子为钒、铬、锰、铁、钴、镍、铜、钌、钯、银、镉、铱、铅中的一种或二种以上,金属盐中阴离子选自硝酸根离子、亚硝酸根离子、硫酸根离子、亚硫酸根离子、硫离子、碳酸根离子、碳酸氢根离子、磷酸根离子、磷酸氢根离子、磷酸二氢根离子、亚磷酸氢根离子、高氯酸根离子、氯酸根离子、次氯酸根离子、氯离子、硼酸根离子、草酸氢根离子、草酸根离子、乙酸根离子、乙酰丙酮根离子中的一种或二种以上。
有机溶剂可以为一切可溶解金属盐有机化合物,具体为:苯、甲苯、二甲苯、氯苯、二氯苯、甲醇、乙醇、异丙醇、环己酮、甲苯环己酮、丙酮、甲基丁酮、甲基异丁酮、乙腈、吡啶中的一种或二种以上。
步骤1)中金属盐与碳基载体的质量比为1:50-10000(优选质量比为1:100-1000),碳基载体与水溶液或有机溶剂的质量比1:10-1000(优选质量比为1:50-100);混合方式为超声和搅拌。
步骤3)中混合物2在空气、氧气、氮气、氩气或氨气(氮原子掺杂)中的一种或几种气氛中300℃~1500℃(优选温度为500~800℃)高温焙烧10min~10h。
步骤1)中所述有机溶剂为能够溶解金属盐的有机化合物;步骤4)中进行酸处理时所用酸为盐酸,硝酸或硫酸中的一种,酸浓度为0.5mol/L~18mol/L,酸处理时温度为20-80℃。
本发明还提供上述水氧化催化剂于电解水、光电催化分解水、光催化分解水反应中的应用。
本发明的有益效果为:
该方法能够获得碳基材料骨架中负载不同金属物种(如钒、铬、锰、铁、钴、镍、铜、钌、钯、银、镉、铱和铅等)及非金属物种(如氮),其中金属最高含量可以达到1.5wt.%以上,且金属离子主要以单原子形式存在;氮含量可高达7wt.%以上。制备的原子分散的催化剂在化学水氧化或电化学水氧化反应中显示出优越的催化性能。
该方法制备出的催化剂金属离子主要以单原子形式存在。该法制备的原子分散的催化材料在水氧化反应中的催化性能可以和自然界的PSII相媲美,且催化稳定性好,制备成本低廉,具有很强的实际应用性。可以在电催化分解水、光电催化分解水和光催化分解水以及人工光合二氧化碳还原转化过程中,具有广阔的应用前景。
附图说明
图1锰原子分散催化剂(Mn-G)的扫描电镜照片。
图2锰原子分散催化剂(Mn-G)的投射电镜照片。
图3锰原子分散催化剂(Mn-G)的HAADF-STEM电镜照片。
图4商业三氧化二锰和Mn-G电化学水氧化性能测试。电化学工作站:CHI660(上海辰华有限公司);对电极:铂电极;参比电极:甘汞电极;电解液:1M KOH;扫描速率:50mV·s–1。
图5原子分散催化剂Mn-G电化学稳定性测试。电化学工作站:CHI660(上海辰华有限公司);对电极:铂电极;参比电极:甘汞电极;电解液:1M KOH;扫描速率:50mV·s–1。
图6Mn-G-2的电化学水氧化性能测试。电化学工作站:CHI660(上海辰华有限公司);对电极:铂电极;参比电极:甘汞电极;电解液:1M KOH;扫描速率:50mV·s–1。
图7Mn-G-3的电化学水氧化性能测试。电化学工作站:CHI660(上海辰华有限公司);对电极:铂电极;参比电极:甘汞电极;电解液:1M KOH;扫描速率:50mV·s–1。
图8Cr-G、Fe-G、Co-G和Ni-G的电化学水氧化性能测试。电化学工作站:CHI660(上海辰华有限公司);对电极:铂电极;参比电极:甘汞电极;电解液:1M KOH;扫描速率:50mV·s–1。
图9原子分散催化剂Mn-G在光催化分解水中的应用。测试条件:0.15g催化剂,150mL水,5mM NaIO3,300W氙灯。产生的氧气用安捷伦色谱分析。
图10原子分散催化剂Mn-G在光电分解水中的应用。测试条件:电化学工作站:CHI660(上海辰华有限公司);对电极:铂电极;参比电极:甘汞电极;电解液:0.5M硼酸锂缓冲溶液(pH 9);光源:100mW·cm-2AM1.5G;扫描速率:50mV·s–1。
具体实施方式
为了进一步说明本发明,列举以下实施例,但它并不限制各附加权利要求所定义的发明范围。
实施例1
将40mg硝酸锰、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氨气中700℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的硝酸溶液中80℃搅拌一个小时,过滤,水洗,于80℃干燥,即为锰原子分散的催化剂(Mn-G)。催化剂中锰含量为0.1%左右。性能见表1。
从图1到图3中给出的扫描和投射及球差投射电镜中可以发现我们合成的催化剂中金属锰主要为原子级分散在石墨烯骨架当中。
实施例2
将40mg硝酸铁、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氨气中500℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的硝酸溶液中80℃搅拌一个小时,过滤,水洗,于80℃干燥,即为铁原子分散的催化剂(Fe-G)。性能见图8。
实施例3
将40mg硝酸镍、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氨气中500℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的硝酸溶液中80℃搅拌一个小时,过滤,水洗,于80℃干燥,即为镍原子分散的催化剂(Ni-G)。性能见图8。
实施例4
将40mg硝酸钴、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氨气中500℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的硝酸溶液中80℃搅拌一个小时,过滤,水洗,于80℃干燥,即为钴原子分散的催化剂(Co-G)。性能见图8。
实施例5
将40mg硝酸铬、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氨气中500℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的硝酸溶液中80℃搅拌一个小时,过滤,水洗,于80℃干燥,即为铬原子分散的催化剂(Cr-G)。性能见图8。
实施例6
将20mg硝酸锰、20mg硝酸钴、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氨气中500℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的硝酸溶液中80℃搅拌一个小时,过滤,水洗,于80℃干燥,即为锰-钴原子分散的催化剂(Mn-Co-G)。性能见表1。
实施例7
将40mg氯化锰、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氮气中600℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的盐酸溶液中60℃搅拌一个小时,过滤,水洗,于80℃干燥,即为锰原子分散的催化剂(Mn-G-2)。性能见图6。
实施例8
将40mg氯化锰、0.5g氧化石墨烯和100mL水于250mL烧杯中超声处理4个小时,再于室温下搅拌4个小时使其混合均匀,之后将混合物于空气中80℃干燥。最后将得到的固体研磨成粉末,在氩气中500℃焙烧4个小时得到黑色的粉末。将所得的黑色粉末于5mol/L的硫酸溶液中40℃搅拌一个小时,过滤,水洗,于80℃干燥,即为锰原子分散的催化剂(Mn-G-3)。性能见图7。
比较例1
上述制备的催化材料在水氧化反应中进行测试评价。测试条件为:Strathkelvin782氧气传感器,1mg催化剂,0.15M Ce(NH4)2(NO3)6,总体积3.0mL。从表1可以看出相比于商业三氧化二锰,单原子锰催化剂在水氧化反应中的催化活性提高了近7个数量级。
表1不同氧化剂的水氧化催化性能比较a
催化剂 | 氧化剂 | TOF s<sup>-1</sup> |
商业三氧化二锰 | Ce(IV) | 2.7*10<sup>-5</sup> |
商业二氧化锰 | Ce(IV) | 3.2*10<sup>-5</sup> |
商业四氧化三钴 | Ce(IV) | 1.4*10<sup>-4</sup> |
PSII | sunlight | 100-400 |
Mn-Co-G | Ce(IV) | 88 |
Mn-G | Ce(IV) | 214 |
aTOF为每个金属原子上每秒钟转化生成的氧气,其中生成的氧气通过Strathkelvin 782氧气传感器测得。
比较例2
上述制备的催化材料在电化学水氧化反应中进行测试评价。测试条件为:上海辰华仪器有限公司生成的电化学工作站,催化剂负载量为40mg/cm2,电解液为1M KOH。从图4可以看出相比于商业三氧化二锰,原子分散的催化剂Mn-G具有更好的是电化学水氧化性能。此外,图5中可以看出原子分散的催化剂Mn-G在电化学水氧化反应中展示出较稳定的催化性能。
相比于一般方法制备的催化剂,本发明制备的单原子催化材料在水氧化反应中的催化性能提高了近七个数量级,具有很高的实用价值。
比较例3
上述制备的催化材料在电化学水氧化反应中进行测试评价。测试条件为:上海辰华仪器有限公司生成的电化学工作站,催化剂负载量为40mg/cm2,电解液为1M KOH。从图8可以看出原子分散的催化剂Cr-G、Fe-G、Co-G和Ni-G都具有良好的是电化学水氧化性能。
比较例4
上述制备的催化材料在光催化分解水中进行测试评价。通过图9不难看出在二氧化钛表面负载少量原子分散催化剂Mn-G后其光解水性能有明显的提升。
比较例5
上述制备的催化材料在光电分解水中进行测试评价。通过图10不难看出在钒酸铋表面负载少量原子分散催化剂Mn-G后其光电分解水性能在1.23V vs.RHE处有明显的提升。
Claims (8)
1.一种水氧化催化剂在电解水、光电催化分解水、光催化分解水中的应用,其特征在于:
于碳基载体的骨架中分散单原子形式的金属离子及非金属原子氮,且金属离子、碳原子及氮原子形成稳定的配位键;
催化剂中金属含量为0.01~2.0 wt.%,氮含量为1-8 wt.%;
所述碳基载体选自石墨片、氧化石墨烯、石墨烯、无定型碳、碳纳米管或多孔碳中的一种或二种以上;
金属为钒、铬、锰、铁、钴、镍、铜、钌、钯、铱中的一种或几种。
2.按照权利要求1所述的应用,其特征在于:
权利要求1中的催化剂制备如下步骤:
1)将金属盐与碳基载体在水中混合均匀,得到混合物1;
2)将步骤1所得的混合物1用旋转蒸发或加热蒸发中的任一种方法除去水,得到混合物2;
3)对混合物2进行研磨,之后高温焙烧处理,得到固体粉末;
4)对固体粉末进行酸处理除去生成的氧化物,再过滤、洗涤、干燥,得到原子分散的水氧化催化剂。
3.按照权利要求1所述的应用,其特征在于:
所述金属盐中金属离子为钒、铬、锰、铁、钴、镍、铜、钌、钯、铱中的一种或二种以上,金属盐中阴离子选自硝酸根离子、亚硝酸根离子、硫酸根离子、亚硫酸根离子、硫离子、碳酸根离子、碳酸氢根离子、磷酸根离子、磷酸氢根离子、磷酸二氢根离子、亚磷酸氢根离子、高氯酸根离子、氯酸根离子、次氯酸根离子、氯离子、硼酸根离子、草酸氢根离子、草酸根离子、乙酸根离子、乙酰丙酮根离子中的一种或二种以上。
4.按照权利要求1所述的应用,其特征在于:
步骤1)中金属盐与碳基载体的质量比为1:50-10000,碳基载体与水质量比为1:10-1000;混合方式为超声和搅拌。
5.按照权利要求4所述的应用,其特征在于:
金属盐与碳基载体的质量比为1:100-1000,碳基载体与水质量比为1:50-100。
6.按照权利要求1所述的应用,其特征在于:
步骤3)中混合物2在氨气气氛中300℃~1500℃高温焙烧10min~10h。
7.按照权利要求6所述的应用,其特征在于:
混合物2在氨气气氛中500℃~800℃高温焙烧10min~10h。
8.按照权利要求1所述的应用,其特征在于:
步骤4)中进行酸处理时所用酸为盐酸,硝酸或硫酸中的一种,酸浓度为0.5 mol/L~18mol/L,酸处理时温度为20-80℃。
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