CN112479158A - 一种甲醇产氢气的方法 - Google Patents
一种甲醇产氢气的方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000001257 hydrogen Substances 0.000 title claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 75
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 29
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种甲醇产氢气的方法,属于化学技术领域。所述方法是以磷化镍/硫化镉材料作为催化剂,将甲醇光催化转化为H2。本发明采用磷化镍/硫化镉光催化剂(NixP/CdS),在室温下有效地将甲醇光催化转化为H2。光催化甲醇分解制氢速率达到约8209.09μmol g‑1h‑1,并且在实际太阳光下同样具有较高的光催化甲醇产氢活性,表明了工业上该复合光催化剂甲醇制氢的可行性。
Description
技术领域
本发明涉及一种甲醇产氢气的方法,属于化学技术领域。
背景技术
环境污染和可持续的绿色能源供应是当今时代全球面临的主要挑战性难题之一。氢气(H2)被认为是工业和日常生活中最绿色的能源,近年来,光催化、电催化和热催化制氢得到了广泛的研究。在上述的产氢技术中,太阳光能是一种丰富、易得的自然能源,在促进环境友好型光化学反应的进行方面拥有巨大的潜力,所以利用光催化技术产生氢能是极具竞争力的。甲醇(CH3OH)是最简单的醇类之一,可以从各种碳源如天然气、页岩气、煤、生物质和二氧化碳中容易地生产出来,并且以其良好的储氢能力(12.6%)、易储存、可再生等优点,作为一种极具发展前景的储氢材料受到了广泛的关注。
过去几十年,甲醇主要通过热催化里甲醇重整(CH3OH+H2O→CO2+H2)和纯甲醇分解(CH3OH→CO+2H2)来转化为氢气。这两种方法是化学工业和氢燃料电池动力装置的基本手段。迄今为止,甲醇重整的催化剂有Pt/Al2O3,Cu/Zn/Al2O3-based,Pt/α-MoC。然而,这些过程的通常条件通常包括高压(20bar)和高温(150℃)、贵金属催化剂和生成COx引起的催化剂中毒。所以需要设计新型甲醇产氢催化剂以及优化甲醇产氢的条件。作为一种替代方法,光催化被认为是最有前途的甲醇分解产生H2的方法之一。
在光催化驱动反应过程中,受到光激发的半导体内部产生的光生载流子是高能量的,可以局部驱动热催化很难或不可能完成的反应。与其他工业过程相比,光催化甲醇转化是一种有前途的过程,具有温和的操作条件(室温和环境压力)和廉价的能源(光/阳光)等。现有文献报道,大多数光催化反应体系中甲醇一般作为作为空穴清除剂,促进水溶液中光催化制氢能。值得注意的是,甲醇被用作空穴牺牲剂,其主要氧化产物如醛。可以进一步氧化为羧酸,一氧化碳(CO)或二氧化碳。此外,由于甲醇还包含氢源,因此不确定系统中产生的氢是否完全来源于水。因此,探索一种在温和的条件下将甲醇直接脱氢成无水甲醛(CH3OH→HCHO+H2)的催化剂至关重要,光催化剂应该能够从甲醇而不是水中提取氢,以实现化学计量的甲醇分解。
发明内容
为了解决上述问题,本发明采用磷化镍/硫化镉光催化剂(NixP/CdS),在室温下有效地将甲醇光催化转化为H2。光催化甲醇分解制氢速率达到约8209.09μmol g-1h-1,并且在实际太阳光下同样具有较高的光催化甲醇产氢活性,表明了工业上该复合光催化剂甲醇制氢的可行性。并且通过气相色谱和紫外-可见光全光谱对反应生成的气体和反应后的溶液进行表征,得到了光催化甲醇产氢的产物为氢气和甲醛,提高了工业价值。
本发明提供了一种甲醇产氢气的方法,所述方法是以磷化镍/硫化镉材料作为催化剂,将甲醇光催化转化为H2。
在本发明的一种实施方式中,所述反应为:CH3OH→HCHO+H2。
在本发明的一种实施方式中,所述反应条件为:反应温度为20-80℃。
在本发明的一种实施方式中,在黑暗条件下,反应温度为50-80℃。
在本发明的一种实施方式中,在光照条件下,反应温度为20-80℃,优选地,反应温度为40-80℃。
在本发明的一种实施方式中,光的波长范围为200-1300nm。
在本发明的一种实施方式中,能提供相应波长光的均可以作为光源,可以是太阳光,也可以是人造光源,比如氙灯、紫外灯、LED灯、激光等。对光的强度没有特殊要求,光强度大的,沉积速度快些。
在本发明的一种实施方式中,采用光化学沉积法制备磷化镍/硫化镉光催化剂。
在本发明的一种实施方式中,所述磷化镍/硫化镉光催化剂的制备方法是:将硫化镉加入到反应容器中,然后添加分散在溶剂中的氯化镍和次亚磷酸盐,混合均匀后除去反应体系中的氧气,然后后置于光照下搅拌反应,生成磷化镍/硫化镉光催化剂。
在本发明的一种实施方式中,光照时间为5-60min,优选地,光照时间为20-40min。
本发明提供了一种上述方法方法在化工和氢燃料电池方面的应用。
本发明的有益效果:
(1)本发明首次探究了在温和的光催化条件下将纯甲醇直接脱氢,实现甲醇的化学计量分解(CH3OH→HCHO+H2),解决了传统工艺中甲醇催化转化反应条件苛刻的问题,为工业应用提供了可能。
(2)本发明采用磷化镍/硫化镉光催化剂(NixP/CdS),在室温下有效地将甲醇光催化转化为H2。光催化甲醇分解制氢速率达到约8209.09μmol g-1 h-1,并且在实际太阳光下同样具有较高的光催化甲醇产氢活性,表明了工业上该复合光催化剂甲醇制氢的可行性。并且通过气相色谱和紫外-可见光全光谱对反应生成的气体和反应后的溶液进行表征,得到了光催化甲醇产氢的产物为氢气和甲醛,提高了工业价值。
附图说明
图1是NixP-30/CdS复合催化剂在不同加热温度的产氢测试图;
图2是NixP-30/CdS复合催化剂的边光照边加热的产氢测试图;
图3是NixP-30/CdS复合催化剂室外太阳光下的光催化产氢测试图。
图4是NixP-30/CdS复合催化剂在模拟太阳光下的产氢稳定性测试图;
图5是硫化镉纳米球和NixP-T/CdS复合催化剂的XRD图谱;
图6是CdS纳米球(a)和NixP-30/CdS(b)的TEM电镜图像,(c)NixP-30/CdS的HRTEM图像。
图7是NixP-T/CdS复合催化剂的拉曼光谱;
图8是NixP-T/CdS复合催化剂的X射线光电子能谱;(a)P 2p,(b)Ni 2p,(c)Cd 3d,(d)S 2p;
图9是NixP-T/CdS复合催化剂在可见光下的光催化产氢测试图。
具体实施方式
以下对本发明的优选实施例进行说明,应当理解实施例是为了更好地解释本发明,不用于限制本发明。
实施例1:一种甲醇产氢气的方法
取5mg磷化镍/硫化镉复合催化剂置于25mL光催化反应器中,随后加入10mL无水甲醇。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于300W氙光(配有420nm截止滤光片)下照射1h,反应结束后,用热导检测器对产生的氢气进行气相色谱分析(GC7920-GTF2ZA,分子筛,氩气作为载体气体),产氢速率为8209.09μmol·g-1·h-1。
实施例2:一种甲醇产氢气的方法
取5mg磷化镍/硫化镉复合催化剂置于25mL光催化反应器中,随后加入10mL无水甲醇。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于油浴加热(无光照)反应1h,油浴加热温度分别为20℃、30℃、40℃、50℃、60℃和70℃。反应结束后,用热导检测器对产生的氢气进行气相色谱分析(GC7920-GTF2ZA,分子筛,氩气作为载体气体),结果见图1。甲醇产氢是热催化反应,在传统工艺上的产氢条件通常包括高压(≥20bar)和高温(≥150℃),然而,本实施例采用磷化镍/硫化镉催化剂在黑暗条件下,在20、30、40℃下都没有氢气的产生。当温度升至50℃时,才产生了少量的氢气(0.11μmol),继续升温至60℃产氢活性并没有提高很多。
实施例3:一种甲醇产氢气的方法
取5mg磷化镍/硫化镉复合催化剂置于25mL光催化反应器中,随后加入10mL无水甲醇。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于油浴中并在300W氙光(配有420nm截止滤光片)下反应1h,加热温度25℃、30℃、40℃、50℃和60℃。用热导检测器对产生的氢气进行气相色谱分析(GC7920-GTF2ZA,分子筛,氩气作为载体气体),结果见图2。在仅光照的条件下进行了甲醇产氢的实验,反应后温度升至30℃左右,此时甲醇产氢活性为1.02μmol。同时也进行了在30℃加热并且光照条件下进行光催化甲醇产氢,该条件下甲醇产氢活性为1.03μmol。当加热温度变为60℃时,光照甲醇产氢活性(10.19μmol),比仅加热条件下产氢活性(0.12μmol)高了两个数量级。因此,可以推断出甲醇产氢是光与热的协同效应,并受光效应主导。
实施例4:一种甲醇产氢气的方法
取5mg磷化镍/硫化镉复合催化剂置于25mL光催化反应器中,随后加入10mL无水甲醇。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于室外太阳光照射1-6h,地点:江苏无锡,时间:2019年4月8日10:03-16:15,室外温度:17-28℃。用热导检测器对产生的氢气进行气相色谱分析(GC7920-GTF2ZA,分子筛,氩气作为载体气体),结果见图3。NixP-30/CdS光催化剂在阳光照射下仍然显示出良好的光催化活性并持续的产生氢气。
实施例5:一种甲醇产氢气的方法在工业化应用
取5mg磷化镍/硫化镉复合催化剂置于25mL光催化反应器中,随后加入10mL无水甲醇。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于油浴中并在300W氙光(配有420nm截止滤光片)下进行反应,用热导-气相色谱检测反应中生成的氢气,每隔2h使用热导-气相色谱检测反应中生成的氢气并进行一次脱气排除反应体系中氢气,然后继续光照处理,反应24h后催化活性仍无明显降低(见图4)。表明磷化镍/硫化镉是较为稳定的复合光催化剂,并且为工业上甲醇产氢的应用提供了可行性。
实施例6:一种磷化镍/硫化镉的制备方法
按照如下方法制备磷化镍/硫化镉纳米球复合催化剂
(1)取2mmol二水合乙酸镉、2mmol硫脲与80mL5%一水合肼溶液,置于100mL高压反应釜中,将反应釜置于180℃烘箱中水热处理24h,反应结束后将反应釜置于自然条件下降至室温,过滤得到固体并用去离子水洗涤6-8次左右,乙醇洗涤1-2次,将得到固体置于50℃烘箱干燥10h,得到的固体即为硫化镉纳米球。
(2)取50mg硫化镉纳米球置于25mL单口烧瓶中,随后加入2mL氯化镍水溶液(2mg·mL-1),2mL次亚磷酸钠水溶液(10mg·mL-1),11mL去离子水,超声分散处理1min,然后使用氮气脱气40min除去反应体系中氧气。
(3)待脱气完成后,将圆底烧瓶置于300W氙光灯下照射一段时间,将所得固体离心分离,去离子水洗涤3-6次,乙醇洗涤1-3次,将所得固体使用氮气吹干,得到的固体即为磷化镍/硫化镉纳米球复合催化剂,记为NixP-T/CdS,其中T为照射时间,T分别为5min、10min、20min、30min、40min、50min和60min。
将制备的光催化剂进行X射线衍射光谱(XRD)(图5所示),透射电镜(TEM)(图6所示),拉曼图谱(图7所示),X射线光电子能谱(XPS)(图8所示)及其产氢速率(图9所示)。
通过X射线衍射仪(XRD)研究了纯CdS和NixP-30/CdS复合光催化剂的相结构(图5)。所有样品表现出的主要的衍射峰与CdS标准卡片(JCPDS 41-1049)一致。结果表明,NixP助催化剂通过光沉积方法仅是负载在CdS纳米球表面,并没有改变CdS的结构。在XRD图谱中,与纯CdS相比,所有复合光催化剂与纯CdS之间没有显著差异,原因有两个:一方面是NixP纳米颗粒很好地分散在CdS纳米球表面;另一方面可能是由于CdS的衍射峰非常强,且相对少量的NixP分散在CdS表面所致,通过电感耦合等离子体质谱(ICP-MS)分析NixP-30/CdS中磷化镍含量为0.23wt%。
通过TEM电镜和高倍透射电镜来观察NixP-30/CdS的形貌以及组成。图6a为CdS纳米球的TEM电镜图像,可以看出,水热法制备的CdS纳米球的粒径约为50nm左右。从TEM图像(图6b)中可以发现显示NixP纳米颗粒紧密沉积在CdS纳米球的表面上,平均尺寸约为5nm左右。HRTEM图像(图6c)显示了NixP-30/CdS中CdS的晶格条纹,其中0.357nm和0.334nm的晶格间距分别与CdS(100)和(002)晶面相匹配。此外,HRTEM研究表明,NixP-30/CdS的晶格与CdS的晶格特征是相一致的,猜测通过光沉积得到的NixP纳米颗粒可能为无定型结构。根据XPS,TEM等的表征结果,通过光化学方法获得了分散良好的NixP纳米颗粒。
通过拉曼光谱用于证明复合材料的结构(图7)。在300和600cm-1的拉曼峰分别对应于CdS纳米材料的一阶和二阶纵向光学模(LO),并且NixP-T/CdS复合光催化剂没有新的拉曼峰出现。从拉曼光谱可以看出,在光沉积过程中,CdS的结构没有发生明显的变化。
使用XPS光谱分析了复合光催化剂NixP-T/CdS(T=0,30)的表面物种和化学态。在高分辨率的P 2p光谱中(图8a),可以观察到130.1eV和133.6eV的衍射峰,这分别对应于P2p3/2和P 2p1/2轨道。对于Ni 2p轨道来说(图8b),镍元素的特征峰结合能在856.7eV和875.2eV,与NixP中镍的结合能一致。由Ni 2p和P 2p的XPS峰得到通过光沉积成功的在CdS上负载了NixP纳米颗粒。Cd 3d的高分辨率XPS谱(图8c)显示Cd 3d5/2(405.4eV)和Cd 3d3/2(412.1eV)的两个峰值,与S 2p谱(图8d)中S 2p3/2(161.7eV)和S 2p1/2(162.8eV)的峰值相一致,是CdS的典型特征峰。更值得注意的是,通过比较S和Cd元素在CdS和NixP-30/CdS光催化剂中的结合能,Cd与S的结合能基本保持不变,这些结果表明在CdS表面生成了NixP纳米颗粒。
通过设计对照实验探究不同的光化学沉积时间对复合光催化剂产氢活性的影响,并制备得到了一系列复合光催化剂NixP-T/CdS纳米球(T=5,10,20,30,40,50和60min)。光催化甲醇产氢的速率开始时随着光照时间的增加而逐渐提高。当光照时间增至30min时,甲醇产氢速率最优,可达8209.09μmol g-1h-1(图9)。然而随着光照时间的继续变长,产氢速率有下降的趋势,这可能是由于过量负载的NixP影响了CdS的捕光性能。对比纯CdS纳米球,由于光生载流子的快速重组,光催化甲醇产氢性能非常差(54.15μmol g-1h-1)。当负载助催化剂NixP后,由于助催化剂NixP的存在,能够有效地促进了光生载流子的分离和转移,提高了光催化剂的产氢性能。因此,在我们的样品中,最佳照射时间为30min,NixP-30/CdS样品在后续的实验中被广泛使用。
对比例1:
取5mg硫化镉置于25mL光催化反应器中,随后加入10mL无水甲醇。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于300W氙光(配有420nm截止滤光片)下照射,反应1h结束后,用热导-气相色谱检测反应中生成的氢气,产氢速率为54.15μmol·g-1·h-1。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (10)
1.一种甲醇产氢气的方法,其特征在于,所述方法是以磷化镍/硫化镉材料作为催化剂,将甲醇光催化转化为H2。
2.根据权利要求1所述的方法,其特征在于,在催化剂条件下,所述反应为:CH3OH→HCHO+H2。
3.根据权利要求1或2所述的方法,其特征在于,所述反应条件为:反应温度为20-80℃。
4.根据权利要求3所述的方法,其特征在于,在黑暗条件下,反应温度为50-80℃。
5.根据权利要求3所述的方法,其特征在于,在光照条件下,反应温度为40-80℃。
6.根据权利要求5所述的方法,其特征在于,光的波长范围为200-1300nm。
7.根据权利要求1-6任一项所述的方法,其特征在于,采用光化学沉积法制备磷化镍/硫化镉光催化剂。
8.根据权利要求7所述的方法,其特征在于,所述磷化镍/硫化镉光催化剂的制备方法是:将硫化镉加入到反应容器中,然后添加分散在溶剂中的氯化镍和次亚磷酸盐,混合均匀后除去反应体系中的氧气,然后后置于光照下搅拌反应,生成磷化镍/硫化镉光催化剂。
9.根据权利要求8所述的方法,其特征在于,光照时间为5-60min。
10.权利要求1-9任一项所述的方法在化工和氢燃料电池方面的应用。
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