CN107473183B - 磷化钼在碱性甲醛溶液中催化制氢的应用 - Google Patents
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract
磷化钼在碱性甲醛溶液中催化制氢的应用。其催化反应条件是：在室温及加热条件下进行，甲醛水溶液中氢氧化钠浓度在0.01~10 mol·L‑1之间，甲醛溶液浓度在0.1~3 mol·L‑1之间，100 mL甲醛溶液中磷化钼催化剂用量在5~30 mg之间。本发明在惰性气体气氛下制备的氢气可直接用于燃料电池，不必分离氧气。在室温下和加热条件下就可以有效地催化碱性甲醛溶液制氢，为燃料电池提供氢源。在室温下，本发明所述的磷化钼催化碱性甲醛溶液制氢速率达到了150 mL·min‑1·g‑1，是贵金属Pd催化甲醛制氢的2倍，是金属Cu催化甲醛制氢的7倍。在加热条件下，磷化钼催化甲醛制氢速率可以成倍地增加。
Description
技术领域
本发明属于化学应用技术领域，涉及磷化钼的新用途。
背景技术
人类社会的进步与工业的迅速发展使得能源消耗剧增和环境污染加剧。因此，人们一直在寻求新的可持续、清洁的能源。而氢能以其清洁环保的特点受到人们的追捧。经济、安全、环境友好的制氢和储氢是亟待解决的关键技术。氢燃料电池能量转化率高达60%~80%，是利用氢能最理想的方式。燃料电池对氢气的纯度要求很高，不能含CO，否则会使Pt电极中毒。
甲醛是低成本的化学品，能够大规模工业制备。甲醛在氢氧化钠水溶液中可以产生少量的氢气。在催化剂存在下，甲醛在碱性溶液中，能够高效产氢。这种方法产生的氢气很纯净，不含CO和CO2，特别适合氢燃料电池的储氢。Hu等人制备出了钯纳米管，在室温下催化碱性甲醛溶液制氢，在25℃下，反应1 h后产氢量高达80 mL；Li等人发现银纳米颗粒也能够在室温下催化碱性甲醛溶液制氢，在25℃和纯氧条件下，1 h产氢量达到了20 mL，是氮气氛围下的10倍。甲醛产氢反应装置简单，但是目前使用的贵金属催化剂价格昂贵，资源有限。利用非贵金属及化合物价格较低，具有很好的实际应用前景。
磷在地壳含量丰富，列前10位。钼虽然在地壳中的含量不是很高，但它容易成矿，所以它开采和制备成本低于贵金属。用磷化钼替代贵金属作为催化剂分解甲醛制氢具有成本优势和资源优势。以往报导的文献中，磷化钼主要用于油品的加氢脱硫处理，或者作为助催化剂用于电解水制氢和光催化制氢。
发明内容
本发明的目的是提供磷化钼的一种新用途，即磷化钼在碱性甲醛溶液中催化制氢的新用途。
本发明是通过以下技术方案实现的。
本发明所述的磷化钼的化学组成为MoP。
本发明所述的磷化钼在碱性甲醛溶液中催化制氢的应用，是在惰性气体-氮气或氩气氛围下和碱性溶液中，磷化钼催化分解甲醛制氢。
所述的催化反应可在室温及加热条件下进行，优化的反应温度大于45℃。甲醛水溶液中氢氧化钠浓度在0.01~10 mol·L-1之间，优化的浓度在1~4 mol·L-1之间。甲醛溶液浓度在0.1~3 mol·L-1之间，优化的浓度在1~3 mol·L-1之间。100 mL甲醛溶液中磷化钼催化剂用量在5~30 mg之间，优化的用量在20~30 mg。
本发明提供了一种磷化钼在惰性气体氛围下甲醛溶液中制氢的新用途。在惰性气体气氛下制备的氢气可直接用于燃料电池，不必分离氧气。在室温下和加热条件下就可以有效地催化碱性甲醛溶液制氢，为燃料电池提供氢源。在室温下，本发明所述的磷化钼催化碱性甲醛溶液制氢速率达到了150 mL·min-1·g-1，是贵金属Pd催化甲醛制氢的2倍，是金属Cu催化甲醛制氢的7倍。在加热条件下，磷化钼催化甲醛制氢速率可以成倍地增加。
附图说明
图1为实施例1中以不同摩尔比的Na2MoO4和NaH2PO2为反应物制备的磷化钼的X衍射图。
图2为实施例1中以不同摩尔比的Na2MoO4和NaH2PO2为反应物制备的磷化钼在碱性甲醛溶液中催化产氢活性的对比。
图3为实施例2中当Na2MoO4和NaH2PO2摩尔比为1:7时制备的磷化钼在不同碱浓度下催化甲醛溶液产氢活性。
图4为实施例3中当Na2MoO4和NaH2PO2摩尔比为1:7时制备的磷化钼在不同浓度的甲醛溶液中催化产氢活性。
图5为实施例4中当Na2MoO4和NaH2PO2摩尔比为1:7时制备的磷化钼的加入量对碱性甲醛溶液催化产氢活性的影响。
图6为实施例5中当Na2MoO4和NaH2PO2摩尔比为1:7时制备的磷化钼在不同温度下催化碱性甲醛溶液产氢活性。
具体实施方式
本发明将通过以下实施例作进一步说明。但本发明的内容不局限于此。
实施例1。
（1）磷化钼催化剂的制备。按摩尔比为1:3~1:9称取Na2MoO4和NaH2PO2（Na2MoO4的物质量为1毫摩尔），溶解在15 mL水中，搅拌溶解，60℃烘干得到固体反应物前驱体，研磨之后在N2气氛的管式马弗炉中300℃下煅烧1 h。去离子水、乙醇洗涤多次，60℃干燥得到磷化钼。
图1是以不同摩尔比的Na2MoO4和NaH2PO2为反应物制备的磷化钼的X衍射图（XRD）。从图中可以看出，随着NaH2PO2的量的增加，晶型并未发生变化，均为MoP，但XRD图中衍射峰慢慢变弱。
（2）磷化钼催化分解甲醛溶液制氢活性的评价。磷化钼分解甲醛制氢反应在一个约500 mL Pyrex烧瓶中进行，瓶口用硅橡胶密封。称取20 mg上述不同组成的磷化钼，加入到100 mL的甲醛碱性溶液中。该溶液中氢氧化钠和甲醛的浓度均为1.0 mol·L-1。充N2 20min充分排除体系中的氧，25℃下搅拌反应1 h，反应气相产物氢气通过瓶口硅橡间隙取样分析，用气相色谱仪分析（检测器为TCD，载气为N2，分离柱为NaX分子筛柱，外标法定量）。
如图2所示，制备的磷化钼分解甲醛产氢活性随制备催化剂过程中NaH2PO2加入量增加而增加，当Na2MoO4和NaH2PO2摩尔比为1:7以后产氢量增加缓慢，考虑原料成本，优选的Na2MoO4和NaH2PO2摩尔比为1:7。
实施例2。
（1）磷化钼催化剂的制备。称取1 mmol Na2MoO4和7 mmol NaH2PO2，溶解在15 ml水中，搅拌下溶解，60℃烘干得到固体反应物前驱体。研磨之后在N2气氛300℃下煅烧1 h。去离子水、乙醇洗涤多次，60℃干燥得到磷化钼。
（2）氢氧化钠浓度对甲醛制氢反应活性的影响。制氢反应活性的评价同实施例1中步骤（2）。称取20 mg制备的磷化钼加入到1 mol·L-1甲醛溶液的反应液中，该溶液中氢氧化钠的浓度在0.01-4 mol·L-1范围之间。室温（20℃）下搅拌反应30 min。如图3所示，在低的碱浓度下（小于0.5 mol.L-1），产氢活性很低，但当氢氧化钠浓度大于1.0 mol·L-1后，碱浓度对产氢活性的影响很小。优化的氢氧化钠浓度在1-3 mol·L-1之间。
实施例3。
（1）催化剂的制备同实施例2步骤1。
（2）甲醛浓度对甲醛制氢反应活性的影响。制氢反应活性的评价同实施例1中步骤2。称取20 mg制备的磷化钼加入到1 mol·L-1氢氧化钠溶液的反应液中，该反应液甲醛的浓度在0.1-3 mol·L-1范围之间。室温（20℃）下搅拌反应30 min。如图4所示，产氢活性随着甲醛浓度的增加而增加，在甲醛浓度为2 mol·L-1时达到最佳。优化的甲醛浓度在1-3 mol·L-1之间。
实施例4。
（1）催化剂的制备同实施例2步骤1。
（2）磷化钼的量对甲醛制氢反应活性的影响。制氢反应活性的评价同实施例1中步骤（2）。称取5-30 mg制备的磷化钼加入到100 mL的甲醛碱性溶液中，甲醛和氢氧化钠的浓度均为1.0 mol·L-1。室温（20℃）下搅拌反应30 min。如图5所示，产氢活性随着加入的磷化钼的量增加而增加，在磷化钼的量达到20 m g时产氢最佳，高于20 mg后产氢量略微下降。优化的磷化钼的量在20-30 mg之间。
实施例5。
（1）催化剂的制备同实施例2步骤1。
（2）反应温度对甲醛制氢活性的影响。制氢反应活性的评价同实施例1中步骤（2）。称取20 mg制备的磷化钼加入到100 mL的甲醛碱性溶液中，甲醛和氢氧化钠的浓度均为1.0mol·L-1。反应温度控制在5-65℃之间，搅拌反应10 min。如图6所示，产氢活性随反应温度增加而增加，当温度高于45℃后，产氢活性迅速增加。考虑到实际应用中应尽可能采用低温, 优化的反应温度应高于45℃。
Claims (1)
1.磷化钼在碱性甲醛溶液中催化制氢的应用，在惰性气体-氮气或氩气氛围下和碱性溶液中，磷化钼催化分解甲醛制氢；催化反应条件是：
在室温及加热条件下，甲醛水溶液中氢氧化钠浓度在0.01~10 mol·L-1之间，甲醛溶液浓度在0.1~3 mol·L-1之间，100 mL甲醛溶液中磷化钼催化剂用量在5~30 mg之间；
反应温度大于45℃，甲醛水溶液中氢氧化钠浓度在1~4 mol·L-1之间，甲醛溶液浓度在1~3 mol·L-1之间，100 mL甲醛溶液中磷化钼催化剂用量在20~30 mg之间。
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