CN110193374A - 硼碳氮电催化材料及其制备方法和在氮还原合成氨中的应用 - Google Patents
硼碳氮电催化材料及其制备方法和在氮还原合成氨中的应用 Download PDFInfo
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Abstract
一种硼碳氮电催化材料及其制备方法和在氮还原合成氨中的应用,所述硼碳氮电催化材料具有纳米尺度的镂空网格形貌结构,均匀分布在可裁剪的碳纸衬底上,其制备方法为(1)将尿素、硼酸和聚乙二醇完全溶解于去离子水中,加入碳纸衬底,使碳纸衬底上分布上硼酸、尿素和聚乙二醇的混合物,将碳纸衬底蒸干水分;(2)将碳纸衬底置于置于程序升温管式炉中,在氩气气氛下,煅烧得到硼碳氮电催化合成氨材料。本发明的材料具有稳定性强、耐化学腐蚀、耐高温及电导性好等特征,可在较低电压下实现电催化还原N2至NH3,催化稳定性良好。该催化材料的原料低廉易得、合成工艺简单、容易大规模生产,催化性能优越,十分适于在电催化合成氨领域中应用。
Description
技术领域
本发明涉及一种硼碳氮电催化材料及其在氮还原合成氨中的应用,属于电催化剂技术领域。
背景技术
作为一种重要的化工产品,氨在化工产业中占有着不可或缺的地位。自20世纪初Haber-Bosch合成氨的方法诞生以来,科研工作者不断对催化合成氨技术工艺进行革新,研制新的催化剂及助催化剂尝试降低合成氨的温度和压力并提高氮转氨的转化率。但是,随着能源问题和环境问题的日益凸显,探索高效率、低能耗和环境友好的合成氨新方法成了可持续发展的必然要求。考虑到氮转氨的反应本质,充足的电子(e-)和质子(H+或H.)源可以促进氨的合成,反应方程式:N2+6H++6e-→2NH3。基于此,电催化合成氨成为了一种潜在的新方法。该方法具有反应温和、能耗低、环境友好等优势。然而电催化合成氨仍然有诸多不足,如法拉第效率不高,反应环境苛刻,催化剂易失活等。
为了解决上述问题,催化剂的选择和使用至关重要。目前的低温电催化合成氨催化剂多为金属催化剂。过渡金属是促进N≡N断裂的关键组分,N≡N的反键π轨道可由过渡金属提供的外层电子加速N≡N的断裂,从而达到提高合成氨速率的目的。但是,金属易过渡吸附活性氢。鉴于此,寻找一种既可促进N≡N键断裂又可以抑制H2的竞争吸附的催化剂成为催化剂领域的研究热点。研发制备新型高效的中性条件稳定高效催化固氮的非金属电催化剂迫在眉睫。
发明内容
本发明旨在提供一种硼碳氮电催化材料及其在氮还原合成氨中的应用。
本发明的硼碳氮电催化材料,其具有纳米尺度的镂空网格形貌结构,分布在碳纸衬底上。均匀分布,碳纸衬底可裁剪。
上述硼碳氮电催化材料的合成方法,包括以下步骤:
(1)将尿素、硼酸和聚乙二醇完全溶解于去离子水中,加入碳纸衬底,使碳纸衬底上分布上硼酸、尿素和聚乙二醇的混合物,将碳纸衬底蒸干水分;
所述聚乙二醇为聚乙二醇1000,1500,2000,3000或4000。所述硼酸和聚乙二醇的质量比为0.15:0.5~8,所述尿素和硼酸的摩尔比为1~10:1。所加碳纸衬底尺寸为1cm×2cm~ 10cm×10cm。所述碳纸衬底蒸干水分是在80℃和常压条件下进行。
(2)将碳纸衬底置于程序升温管式炉中,在氩气气氛下,通过程序升温煅烧得到硼碳氮电催化合成氨材料。
所述程序升温速率为2℃/min~10℃/min,起始温度为室温,保持温度为900℃~1100℃,保温时间为1小时~5小时。
上述硼碳氮电催化材料按以下方式应用于氮还原合成氨:
硼碳氮材料为工作电极,以Pt为对电极,Ag/AgCl为参比电极,采用三电极反应装置,在电场辅助下,在不同电压下氮还原合成氨。
本发明首次通过简单的煅烧方式合成硼碳氮材料,制备成本低廉,操作简便,并将这种材料作为固氮电催化剂应用于电催化合成氨。该电催化材料合成氨的产率为8.2μg·h-1·cm-2,法拉第效率为7%,且具有非常好的催化稳定性。
附图说明
图1为本发明制备的硼碳氮电催化材料的扫描电镜图。
图2为本发明制备的硼碳氮电催化材料的透射电镜图。
图3为本发明制备的硼碳氮电催化材料的XPS图。
图4为本发明制备的硼碳氮电催化材料的傅氏转换红外线光谱图。
图5为本发明制备的硼碳氮电催化材料的不同电位下固氮性能图。
图6为本发明制备的硼碳氮电催化材料的不同电位下法拉第效率图。
图7为本发明制备的硼碳氮电催化材料的不同气氛下固氮性能图。
图8为本发明制备的硼碳氮电催化材料的性能稳定性图。
具体实施方式
实施例1
(1)前驱体合成
将6g尿素(10mmol),0.15g硼酸(2.5mmol)和1.5g聚乙二醇4000溶于去离子水中,完全溶解,加入5cm×5cm的碳纸衬底,随后于80℃、常压条件下蒸干所有水分。
(2)煅烧制备最终产物
均匀分布尿素、硼酸和聚乙二醇4000混合物的碳纸置于刚玉瓷舟中,再将其置于程序升温管式炉中,在氩气气氛下,煅烧得到硼碳氮电催化合成氨材料。在氩气气氛中,升温速率为5℃/min,起始温度为室温,保持温度为950℃,保温时间为2小时,反应后自然降温,制得硼碳氮电催化材料。
通过图1和图2给出的扫描电镜图以及透射电镜图观察,可看出该样品结构为纳米尺度的镂空网格形貌结构。图3和图4给出的XPS图和红外光谱图,可确定材料中BCN三种元素的相互成键(B-C,B-N,C=N)。基于以上表征结果可以确认产物是硼碳氮电催化材料。
将上述方法制备得到的硼碳氮电催化材料应用于电催化氮还原合成氨,其具体步骤为:在气体饱和的0.1mol/L Na2SO4溶液中,采用三电极反应装置,Pt为对电极,Ag/AgCl为参比电极,材料电极做工作电极,在电场辅助下,测试电催化固氮合成氨随电压的变化,如图 6-8所示;图5为不同电位下固氮性能对比,从图中可以看出,最佳电压为-0.6V,合成氨的产率为8.2μg·h-1·cm-2。图6为不同气氛下固氮性能对比,从图中可以看出,氩气气氛下几乎没有产氨性能,氮气饱和溶液中产率明显高于氩气饱和溶液。图7为相应的法拉第效率,在 -0.3V下法拉第效率达到了7%。图8的稳定性图显示其在多次循环后均保持稳定的产率和法拉第效率。综上,该硼碳氮电催化材料具有良好的电催化氮还原合成氨性能。
实施例2
如实施例1所述,不同之处在于步骤(1)中聚乙二醇采用聚乙二醇2000。前驱体合成过程中所需添加原料量6g尿素(10mmol),0.15g硼酸(2.5mmol)和1.5g聚乙二醇2000。
实施例3
如实施例1所述,不同之处在于步骤(1)中聚乙二醇采用聚乙二醇1000。前驱体合成过程中所需添加原料量6g尿素(10mmol),0.15g硼酸(2.5mmol)和0.5g聚乙二醇1000。
实施例4
如实施例1所述,不同之处在于步骤1)中聚乙二醇采用聚乙二醇3000。前驱体合成过程中所需添加原料量6g尿素(10mmol),0.15g硼酸(2.5mmol)和8g聚乙二醇3000。
实施例5
如实施例1所述,不同之处在于步骤(1)中尿素和硼酸摩尔比为1:1。前驱体合成过程中所需添加原料量1.5g尿素(2.5mmol),0.15g硼酸(2.5mmol)和3g聚乙二醇1500。
实施例6
如实施例1所述,不同之处在于步骤(1)中尿素和硼酸摩尔比为10:1。前驱体合成过程中所需添加原料量15g尿素(25mmol),0.15g硼酸(2.5mmol)和6g聚乙二醇4000。
实施例7
如实施例1所述,不同之处在于步骤(1)中碳纸衬底大小为1cm×2cm。
实施例8
如实施例1所述,不同之处在于步骤1)中碳纸衬底大小为10cm×10cm。
实施例9
如实施例1所述,不同之处在于步骤(2)中升温速率为2℃/min。
实施例10
如实施例1所述,不同之处在于步骤(2)中升温速率为10℃/min。
实施例11
如实施例1所述,不同之处在于步骤(2)中保持温度为900℃。
实施例12
如实施例1所述,不同之处在于步骤(2)中保持温度为1100℃。
实施例13
如实施例1所述,不同之处在于步骤(2)中保持时间为1小时。
实施例14
如实施例1所述,不同之处在于步骤(2)中保持时间为5小时。
本发明通过简单锻烧的方法得到了硼碳氮电催化材料,通过扫描电子显微镜和透射电子显微镜表征了纳米网格形貌,通过元素分布确定了三种元素的均匀排布,通过XPS和红外光谱证实了其为硼碳氮电催化材料。将所制备的材料用作工作电极,其表现出优异的电催化合成氨活性,且材料电极保持了高稳定性,因此本发明材料在电催化合成氨领域存在重要应用价值。
Claims (8)
1.一种硼碳氮电催化材料,其特征是:具有纳米尺度的镂空网格形貌结构,分布在碳纸衬底上。
2.一种权利要求1所述硼碳氮电催化材料的合成方法,其特征是:包括以下步骤:
(1)将尿素、硼酸和聚乙二醇完全溶解于去离子水中,加入碳纸衬底,使碳纸衬底上分布上硼酸、尿素和聚乙二醇的混合物,将碳纸衬底蒸干水分;
(2)将碳纸衬底置于程序升温管式炉中,在氩气气氛下,通过程序升温煅烧得到硼碳氮电催化合成氨材料。
3.根据权利要求2所述硼碳氮电催化材料的合成方法,其特征是:所述聚乙二醇为聚乙二醇1000,1500,2000,3000或4000。
4.根据权利要求2所述硼碳氮电催化材料的合成方法,其特征是:所述硼酸和聚乙二醇的质量比为0.15:0.5~8,所述尿素和硼酸的摩尔比为1~10:1。
5.根据权利要求2所述硼碳氮电催化材料的合成方法,其特征是:所加碳纸衬底尺寸为1cm×2cm~10cm×10cm。
6.根据权利要求2所述硼碳氮电催化材料的合成方法,其特征是:所述碳纸衬底蒸干水分是在80℃和常压条件下进行。
7.根据权利要求2所述硼碳氮电催化材料的合成方法,其特征是:所述程序升温速率为2℃/min~10℃/min,起始温度为室温,保持温度为900℃~1100℃,保温时间为1小时~5小时。
8.权利要求1所述硼碳氮电催化材料的应用于氮还原合成氨,硼碳氮材料为工作电极,以Pt为对电极,Ag/AgCl为参比电极,采用三电极反应装置,在电场辅助下,在不同电压下氮还原合成氨。
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