CN111617776A - 富CO2气氛下催化CO氧化的Au/M1-M2-Ox/Al2O3纳米金催化剂 - Google Patents
富CO2气氛下催化CO氧化的Au/M1-M2-Ox/Al2O3纳米金催化剂 Download PDFInfo
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Abstract
本发明涉及一种富CO2气氛下催化CO氧化的Au/M1‑M2‑Ox/Al2O3纳米金催化剂。本发明通过添加M1Ox、M2Ox的方法对Al2O3载体改性,制备出强碱位点较少且富含活性氧物种的M1‑M2‑Ox/Al2O3载体,进而制备出Au/M1‑M2‑Ox/Al2O3催化剂。在60 vol.% CO2气氛中进行测试,评价其活性和稳定性。实验结果表明,本发明催化剂在富CO2气氛中的CO催化氧化活性高,并具有极好的抗CO2累积能力,反应稳定性优异,在CO2激光器等富CO2场景中有良好的应用潜力。
Description
技术领域
本发明涉及一种能在富CO2气氛下使用的,高分散、高稳定性的Au/M1-M2-Ox/Al2O3纳米金催化剂及其应用。具体是通过添加M1Ox、M2Ox的方法制备出了一系列对惰性载体改性的强碱位点较少且富含活性氧物种的金属氧化物复合载体,以及该新型催化剂在富CO2气氛下的应用。
背景技术
负载型纳米金催化剂对CO氧化反应具有良好的催化性能,能够在低温下将CO氧化为 CO2,但在反应过程中催化剂易失活。研究表明原因之一是由于CO2在催化剂表面生成了碳酸盐物种,碳酸盐物种不断累积且与催化剂表面的Au活性位点重叠,从而阻碍了反应的进行并导致反应活性迅速下降。在富CO2气氛下进行的CO氧化反应,如CO-PROX(约20vol.%),CO2激光器(约60 vol.%),更容易造成碳酸盐物种积累,从而极大的降低了金催化剂的活性和稳定性。因此,亟待发明一种能在富CO2气氛下使用的高分散、高稳定性的纳米金催化剂。
由于高的比表面积和热稳定性,Al2O3作为载体广泛应用于催化剂制备过程中。申请人所在的烟台大学化学与化工学院也一直致力于以Al2O3作为载体的纳米金催化剂的研究与应用开发。已授权专利(1、安立敦, 齐世学, 邹旭华, 催化性能稳定的负载型金催化剂及其制备方法,ZL 200410024509.6 WO 2006/007774 A1;2、安立敦,齐世学,林清泉,邹旭华,储存性能稳定的负载型金-PGM合金催化剂及其制备方法, ZL200910019345.0;3、邹旭华,齐世学,安立敦,索掌怀,林清泉,纳米贵金属催化剂的制备方法,ZL201010189525.6)。同时,相比于其他碱性载体,Al2O3含有许多的酸性位点,具有一定的抗CO2累积能力,因此我们采用Al2O3作为载体研发富CO2气氛下具有高活性、高稳定性的纳米金催化剂。
发明内容
本发明所解决的技术问题是提供一种富CO2气氛下催化CO氧化的Au/M1-M2-Ox/Al2O3纳米金催化剂及其制备方法。本发明首先通过M1和M2两种金属对载体进行改性,同时实现对Au纳米粒子的限域,得到的Au纳米粒子平均粒径为2.8 nm左右,促使Au催化剂抗碳酸盐累积能力得到提高,在富CO2气氛下进行CO氧化反应中具有高活性的同时保持较高的反应稳定性。
本发明实施方案如下:
富CO2气氛下催化CO氧化的Au/M1-M2-Ox/Al2O3纳米金催化剂,其特征在于,所述催化剂包括活性组分和复合载体,并且所述活性组分为Au,所述复合载体为M1-M2-Ox/Al2O3,其中,M1-M2为Fe-Ce,Fe-Mn,Ni-Nb,Ni-Cr,x=1~3;Au元素占所述催化剂总质量百分比为0.1%~5%,所述复合载体M1-M2-Ox/Al2O3中M1-M2-Ox为Al2O3质量的1~25%,M1和M2的质量比 1: 0.1 ~10。
所述的纳米金催化剂的制备方法,采用沉积沉淀法制备催化剂。
优选,所述的制备方法,包括如下步骤:
(1)称取Al2O3粉末溶于离子水中并充分混匀,加入M1(NO3)x溶液和M2(NO3)x溶液并充分混匀10 oC~80 oC反应2~5h;减压过滤上述悬浊液,将滤饼置于烘箱中100 oC~120 oC干燥2~4h,并在550 oC~850 oC下焙烧2~6 h,研磨,得到M1-M2-Ox/Al2O3复合载体,
其中,M1Ox与M2Ox的质量比为1: 0.1~10, M1-M2-Ox与Al2O3的质量比为1: 10~50;
(2)室温下,称取 M1-M2-Ox/Al2O3粉末溶于离子水中,加入碱溶液调pH值至9~10并充分混匀,加入HAuCl4溶液并充分混匀,其中,碱溶液为NH3•H2O、NH4HCO3、Na2CO3、NaOH、K2CO3、KOH溶液中的一种,Au与M1-M2-Ox/Al2O3的质量比为1:95~999;减压过滤上述悬浊液,超纯水洗涤至滤液中无氯离子;将滤饼置于烘箱中50 oC~70 oC干燥过夜即得。
优选,步骤(1)为浸渍法,具体方法为:将M1(NO3)x溶液与M2(NO3)x溶液混合并摇匀,然后加入Al2O3载体,充分混匀,干燥,550 oC~850 oC下焙烧2~6 h,得到M1-M2-Ox/Al2O3复合载体,
其中,M1Ox与M2Ox的质量比为1: 0.1~10, M1-M2-Ox与Al2O3的质量比为1: 10~50。
在相同的测试条件下,对本发明制备的Au/M1-M2-Ox/Al2O3 催化剂与未改性的Au/Al2O3催化剂进行测试,测试反应条件是:反应压力为常压,反应原料气为体积百分数为1%CO、0.5% O2、60% CO2,平衡气为惰性气体N2的混合气,所述催化剂催化CO氧化成CO2的温度为30~400℃。测试结果显示,与未改性的催化剂相比,所述催化剂的CO氧化反应速率能达到Au/Al2O3催化剂的4-20倍。
与已有技术相比,本发明的实质性特点在于本发明的富CO2气氛下的CO负载型纳米金催化剂参与反应的晶格氧物种途径和抗碳酸盐累积能力大大提高,从而提升了催化剂在富CO2气氛下CO氧化反应中的催化活性和反应稳定性,进一步分析原因在于经M1-M2-Ox改性后催化剂表面的强碱性位点数量降低,同时,M1-M2-Ox中的部分活泼晶格氧物种参与反应,增加了新的反应路径,进而使得本发明的催化剂在富CO2气氛中能有效的抵抗碳酸盐累积,大幅度提高催化剂活性和稳定性。
与已有技术相比,本发明还具有以下优点:
1、本发明所得的纳米金催化剂的Au分散度很高,平均粒径较小(3 nm左右)且分布很窄,而且所用制备方法比较简单、易于规模生产;
2、本发明专利所述催化剂的改性后富含能参与反应的活泼晶格氧物种,使其催化反应活性显著提高,且能够在CO氧化反应中长时间保持较高CO转化率。
3、本发明专利所述催化剂的改性后强碱性位点大大减少,提高了抗碳酸盐累积能力,且能够在CO氧化反应中长时间保持较高CO转化率。
4、本发明专利采用添加金属氧化物助剂的策略制备的Au/M1-M2-Ox/Al2O3催化剂的初始活性高于未改性的Au/Al2O3催化剂,而且其反应稳定性显著优于未改性的催化剂。
附图说明
附图用来提供对本发明技术方案的进一步理解,并且构成说明书的一部分,与本申请的具体实施方式一起用于解释本发明的技术方案,并不构成对本发明技术方案的限制。
图1为实施例1催化剂的TEM照片及其Au纳米粒子的粒径分布。
图2为实施例1催化剂的HADDF-STEM照片及其mapping照片。
图3为实施例1催化剂与对比例1催化剂的活性对比, 模型反应的原料气组成: 60vol.% CO2+1 vol.% CO+0.5 vol.% O2, balanced N2; GHSV: 1, 200, 000 mL.g-1.h-1,Cat.: 0.01g,反应温度:220 oC。
图4为实施例1催化剂与对比例1催化剂的O2-TPD对比。
图5为实施例1催化剂与对比例1催化剂的CO2-TPD对比。
具体实施方式
实施例1
1%Au/8wt.%/Fe-Ce-Ox/Al2O3的制备:
将0.20ml的Ce(NO3)2溶液(0.601mol/L)与0.19 ml的Fe(NO3)3溶液混合并用去离子水稀释至1.5毫升;将0.92g γ-Al2O3与溶液充分混合,老化数小时;将样品在120℃下干燥2h,然后在650 oC下煅烧4小时,获得的复合载体为Fe-Ce-Ox/Al2O3,研成粉末。将0.516 gHAuCl4溶液(19.12 gAu/L)置于烧杯中,滴加氨水将其pH值调节至9;将Fe-Ce-Ox/Al2O3载体添加到溶液中并搅拌数小时;去离子水冲洗样品以除去残留的氯离子,并在70 ℃的空气中干燥数小时,获得的样品为Au/Fe-Ce-Ox/Al2O3。其中, TEM照片及其Au纳米粒子的粒径分布如图1所示,图1显示黑色的Au纳米粒子高度分散,平均粒径较小(2.85±0.48 nm)且分布很窄。从图2中可以看出,Au的分布与Fe-Ce-Ox的分布高度一致,说明Au的分布与Fe-Ce-Ox之前有明显的强相互作用,Fe-Ce-Ox的加入有助于Au颗粒的稳定。
该样品在反应1100分钟以后,在原料气组成为:60 vol.% CO2+1 vol.% CO+0.5vol.% O2, balanced N2; 空速120, 000 mL.g-1.h-1的气氛中,CO转化率仍能达到64%(初始转化率70%),几乎没有下降。
对比例1
1%Au/Al2O3的制备:
将γ-Al2O3粉末在650 oC下煅烧4小时,研成粉末;将0.516 g HAuCl4溶液(19.12 gAu/L.)置于烧杯中,滴加氨水将其pH值调节至9-10;将Al2O3载体添加到溶液中并搅拌数小时;去离子水冲洗样品以除去残留的氯离子,并在70 ℃的空气中干燥数小时,获得的样品表示为Au/Al2O3。
实施例1与对比例1催化活性的对比:
两种催化剂均在220 oC下进行测试,并且催化剂评价前,将实施例1和对比例1干燥好的滤饼分别置于300 oC的H2中原位处理60 min。
原料气组成为:60 vol.% CO2+1 vol.% CO+0.5 vol.% O2, balanced N2; 1,200, 000 mL.g-1.h-1, Cat.: 0.01g。
试验结果如图3所示,实施例1的Au/Fe-Ce-Ox/Al2O3的反应速率和稳定性都好于对比例1的Au/Al2O3催化剂。初始时,Au/Fe-Ce-Ox/Al2O3催化剂的反应速率为0.49 molCO gAu -1 s-1,是Au/Al2O3催化剂的8.6倍(0.057 molCO gAu -1 s-1)。当反应进行到150分钟时, Au/Fe-Ce-Ox/Al2O3催化剂的反应速率为0.46 molCO gAu -1 s-1,几乎是Au/Al2O3 (0.025 molCO gAu -1 s-1)的18倍。
实施例1与对比例1的富CO2气氛下进行CO氧化反应活性试验表明,本发明制备的负载型纳米金催化剂相比现有催化剂在CO2气氛下对CO具有高活性的同时保持较高的反应稳定性。以实施例1的催化剂为例分析原因在于本发明制备的Au/M1-M2-Ox/Al2O3催化剂富含参与反应的活泼晶格氧物种以及强碱性点位减少进而显著提高抗碳酸盐累积能力,使得本发明的Au/M1-M2-Ox/Al2O3 催化剂在富CO2气氛下CO氧化反应中的催化活性和反应稳定性。进一步的,如图4 Au/Fe-Ce-Ox/Al2O3催化剂与Au/Al2O3催化剂的O2-TPD谱图所示,Au/Fe-Ce-Ox/ Al2O3催化剂在300 ~ 600 oC的脱附峰属于活泼晶格氧物种,在该区域内Au/Fe-Ce-Ox/Al2O3催化剂的峰面积增加了200%,说明经Fe-Ce-Ox修饰后催化剂表面富含大量的活泼晶格氧物种,从而能加快反应速率;同时,如图5 Au/Fe-Ce-Ox/Al2O3催化剂与Au/Al2O3催化剂的CO2-TPD谱图所示,Au/Fe-Ce-Ox/Al2O3催化剂在高温(>500 oC)区域相比表面强碱性位点大大减少,使得催化剂表面更不容易积累碳酸盐,使得本发明的催化剂稳定性更好,即发明的催化剂通过M1-M2-Ox改性减少催化剂表面的强碱性位点的同时增加M1-M2-Ox中的部分活泼晶格氧物种参与反应,进而使得本发明催化剂在富含CO2气氛下对CO具有高活性的同时保持较高的反应稳定性。
为进一步证明本发明催化剂在富CO2气氛下进行CO氧化反应的活性,提供下述优选实施例。
实施例2
1%Au/7wt.%/ Fe-Mn-Ox/Al2O3的制备:
称取0.93 g Al2O3粉末溶于30 mL离子水中并充分混匀,加入0.50 mL Fe(NO3)3溶液(0.612 mol/L)和0.27 mL Mn(NO3)2溶液(1.4059 mol/L)并充分混匀;减压过滤上述悬浊液,将滤饼置于烘箱中120 oC干燥2 h,并在650 oC下焙烧4 h,研磨,得到Fe-Mn-Ox/Al2O3复合载体。将0.516 g HAuCl4溶液(19.12 gAu/L.)置于烧杯中,滴加氨水将其pH值调节至9;将Fe-Mn-Ox/Al2O3载体添加到溶液中并搅拌数小时;去离子水冲洗样品以除去残留的氯离子,并在70 ℃的空气中干燥数小时,获得的样品表示为Au/Fe-Mn-Ox/Al2O3。该样品在反应1000分钟以后,在原料气组成为:60 vol.% CO2+1 vol.% CO+0.5 vol.% O2, balanced N2; 空速120, 000 mL.g-1.h-1的气氛中,CO转化率仍能达到70%(初始转化率75%),几乎没有下降,其反应速率为0.59 molCO gAu -1 s-1。
实施例3
1%Au/5wt.%/ Ni-Nb-Ox/Al2O3的制备:
将0.44ml的Ni(NO3)2溶液(0.701mol/L)与0.19 ml的Nb(NO3)3溶液(为1.05mol/L)混合并用去离子水稀释至1.5毫升;将0.95g γ-Al2O3与溶液充分混合,老化数小时;将样品在100℃下干燥4h,然后在650 oC下煅烧4小时,获得的复合载体为Ni-Nb-Ox/Al2O3,研成粉末。将0.516 g HAuCl4溶液(19.12 gAu/L.)置于烧杯中,滴加氨水将其pH值调节至10;将Ni-Nb-Ox/Al2O3载体添加到溶液中并搅拌数小时;去离子水冲洗样品以除去残留的氯离子,并在60℃的空气中干燥过夜,获得的样品表示为Au/Ni-Nb-Ox/Al2O3。该样品在反应1200分钟以后,在原料气组成为:60 vol.% CO2+1 vol.% CO+0.5 vol.% O2, balanced N2; 空速120, 000mL.g-1.h-1的气氛中,CO转化率仍能达到65%(初始转化率69%),几乎没有下降,其反应速率为0.50 molCO gAu -1 s-1。
实施例4
1%Au/10wt.%/ Ni-Cr-Ox/Al2O3的制备:
称取0.90g Al2O3粉末溶于30 mL离子水中并充分混匀,加入0.54ml的Ni(NO3)2溶液(1.87mol/L)与0.30 ml的Cr(NO)3溶液(1.05mol/L)并充分混匀;减压过滤上述悬浊液,将滤饼置于烘箱中120 oC干燥2 h,并在550 oC下焙烧4 h,研磨,得到Ni-Cr-Ox/Al2O3复合载体。将0.516 g HAuCl4溶液(19.12 gAu/L.)置于烧杯中,滴加氨水将其pH值调节至8;将Ni-Cr-Ox/Al2O3载体添加到溶液中并搅拌数小时;去离子水冲洗样品以除去残留的氯离子,并在70 ℃的空气中干燥数小时,获得的样品表示为Au/ Ni-Cr-Ox/Al2O3。该样品在反应1200分钟以后,在原料气组成为:60 vol.% CO2+1 vol.% CO+0.5 vol.% O2, balanced N2; 空速120, 000 mL.g-1.h-1的气氛中,CO转化率仍能达到75%(初始转化率78%),几乎没有下降,其反应速率为0.66 molCO gAu -1 s-1。
Claims (4)
1.富CO2气氛下催化CO氧化的Au/M1-M2-Ox/Al2O3纳米金催化剂,其特征在于,所述催化剂包括活性组分和复合载体,并且所述活性组分为Au,所述复合载体为M1-M2-Ox/Al2O3,其中,M1-M2为Fe-Ce,Fe-Mn,Ni-Nb,Ni-Cr,x=1~3;Au元素占所述催化剂总质量百分比为0.1%~5%,所述复合载体M1-M2-Ox/Al2O3中M1-M2-Ox为Al2O3质量的1~25%,M1和M2的质量比 1: 0.1~10。
2.权利要求1所述的纳米金催化剂的制备方法,其特征在于,采用沉积沉淀法制备催化剂。
3.如权利要求2所述的制备方法,其特征在于包括如下步骤:
(1)称取Al2O3粉末溶于离子水中并充分混匀,加入M1(NO3)x溶液和M2(NO3)x溶液并充分混匀10 oC~80 oC反应2~5h;减压过滤上述悬浊液,将滤饼置于烘箱中100 oC~120 oC干燥2~4h,并在550 oC~850 oC下焙烧2~6 h,研磨,得到M1-M2-Ox/Al2O3复合载体,
其中,M1Ox与M2Ox的质量比为1: 0.1~10, M1-M2-Ox与Al2O3的质量比为1: 10~50;
(2)室温下,称取 M1-M2-Ox/Al2O3粉末溶于离子水中,加入碱溶液调pH值至9~10并充分混匀,加入HAuCl4溶液并充分混匀,其中,碱溶液为NH3•H2O、NH4HCO3、Na2CO3、NaOH、K2CO3、KOH溶液中的一种,Au与M1-M2-Ox/Al2O3的质量比为1:95~999;减压过滤上述悬浊液,超纯水洗涤至滤液中无氯离子;将滤饼置于烘箱中50 oC~70 oC干燥过夜即得。
4.如权利要求3所述的纳米金催化剂的制备方法,其特征在于步骤(1)为浸渍法,具体方法为:将M1(NO3)x溶液与M2(NO3)x溶液混合并摇匀,然后加入Al2O3载体,充分混匀,干燥,550 oC~850 oC下焙烧2~6 h,得到M1-M2-Ox/Al2O3复合载体,
其中,M1Ox与M2Ox的质量比为1: 0.1~10, M1-M2-Ox与Al2O3的质量比为1: 10~50。
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