CN111617790A - 一种氮掺杂碳层包覆碳化钴锰复合材料及其应用 - Google Patents
一种氮掺杂碳层包覆碳化钴锰复合材料及其应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 22
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 150000002696 manganese Chemical class 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 13
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 12
- 229960003351 prussian blue Drugs 0.000 claims description 12
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 abstract description 74
- 229910021213 Co2C Inorganic materials 0.000 abstract description 43
- 239000001257 hydrogen Substances 0.000 abstract description 18
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 10
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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Abstract
本发明属于纳米材料及光催化技术领域,特别涉及一种氮掺杂碳包覆的Mn2Co2C复合材料,由包括以下步骤的方法制成:将可溶性正二价钴盐、正二价锰盐与钴氰化钾反应得到沉淀,沉淀在N2气氛保护下高温反应,即得。本发明氮掺杂碳包覆的Mn2Co2C复合材料可作为产氢助催化剂,能够接受电子以及促进析氢反应,将Mn2Co2C@C纳米颗粒作为助催化剂负载在g‑C3N4表面得到g‑C3N4/Mn2Co2C@C复合光催化剂材料,表现出高效的光催化分解水产氢活性。
Description
技术领域
本发明属于纳米材料及光催化技术领域,特别涉及一种氮掺杂碳包覆的Mn2Co2C复合材料及其作为光催化反应助催化剂的应用。
背景技术
化石能源(煤炭、石油、天然气等)是当前全球能源供给的主体。化石能源的消费是环境污染、温室效应的主要因素。另一方面,化石能源的储量是有限的,而人类社会的发展是无限的,人类庞大的能源消耗加速了化石能源的枯竭。环境污染与能源短缺成为人类社会在21 世纪面临的重大问题,寻找可持续性的清洁型替代能源引起了前所未有的关注。太阳能是最具前景的可再生能源,因为它取之不尽、用之不竭、分布广泛。然而,由于太阳辐射的分散性与间歇性,从太阳获取的能量必须有效地转换成可储存、可运输以及可按需使用的化学能(Nat. Mater., 2017, 16, 23-34)。这一需求推动了可持续人工光合作用的发展,目的是模拟自然光合作用,利用太阳能将H2O与CO2转化为燃料(Chem. Soc. Rev.,2009, 38, 253-278)。 在人工光合作用产生的太阳能燃料中,氢能(H2)是最具吸引力的一种,因为它具有高能量密度(每公斤氢气燃烧的热值约为1.4×108 J,其燃烧热值是酒精的3.9倍,是汽油的3倍),且燃烧时不产生污染物。并且H2还可以用作大宗化学品合成的原料。因此,利用太阳能分解水生产H2,为解决能源短缺与环境污染提供了可能。
一般来说,光催化剂表面的H2与O2的生成反应分别由还原与氧化助催化剂驱动(Nature Reviews Materials, 2017, 2, 17050)。其中,功函较大的贵金属Pt容易与半导体形成肖特基势垒,可以作为优良的电子捕获陷阱,由于对质子的良好吸附而促进了H2的生成反应(Chem. Rev. 2020, 120, 2, 919-985)。然而,水分解的逆反应也倾向于发生在Pt纳米颗粒上,因为Pt表现出较低的O2还原反应的过电位(J. Catal. 2008, 259, 133-137)。这个问题可以通过使用Ru(J. Phys. Chem. C 2011, 115, 3057-3064)或Rh(Angew.Chem. Int. Ed. 2006, 45, 7806-7809)替代Pt催化水分解来避免。另外,光催化析氧半反应才是光催化水分解速率的决定步骤,因为它涉及到由H2O形成O2的四电子氧化路径,需要1.23 eV的能量。为了达到高效率的水氧化半反应速率,贵金属氧化物,如RuO2(J. Am.Chem. Soc. 2005, 127, 4150-4151)与IrO2(J. Am. Chem. Soc. 2009, 131, 926-927)等,被认为是最好的析氧助催化剂。虽然这些贵金属与贵金属氧化作为助催化剂具有很高的催化效率,但是其储量有限,且成本高昂,不利于其大规模应用。基于上述考虑,探索基于非贵金属材料的助催化剂用于光催化分解水产氢具有重要的意义。
发明内容
本发明的首要目的在于提供一种氮掺杂碳层包覆的碳化钴锰复合材料,命名为Mn2Co2C@C,可作为产氢助催化剂,能够接受电子以及促进析氢反应,将Mn2Co2C@C纳米颗粒作为助催化剂负载在g-C3N4表面得到g-C3N4/Mn2Co2C@C复合光催化剂材料,表现出高效的光催化分解水产氢活性。
本发明的目的通过下述方案实现:
一种氮掺杂碳层包覆碳化钴锰复合材料,由包括以下步骤的方法制成:将可溶性正二价钴盐、正二价锰盐与钴氰化钾反应得到沉淀,沉淀在N2气氛保护下高温反应,即得。具体为:
(1)制备钴锰普鲁士蓝:将可溶性的正二价钴盐、正二价锰盐溶解在水中,然后加入钴氰化钾,溶解完全后静置一段时间分离得到沉淀,所得沉淀进一步干燥得到钴锰普鲁士蓝;
(2)制备Mn2Co2C@C:将步骤(1)中所得钴锰普鲁士蓝研磨均匀,放入管式炉中在N2气氛保护下高温反应,反应结束后即得Mn2Co2C@C。
所述的可溶性正二价钴盐包括但不限于硝酸钴、硫酸钴、乙酸钴等。
所述的可溶性正二价锰盐包括但不限于硝酸锰、硫酸锰、乙酸锰等。
所述的可溶性正二价钴盐、正二价锰盐的用量满足:正二价钴盐与正二价锰盐的摩尔比为1: 5。
所述的可溶性正二价钴盐和正二价锰盐的总摩尔量与钴氰化钾的摩尔量之比为3:2。
所述的水只是作为反应介质,因此其用量只需要其可以完全溶解所加入的可溶性正二价钴盐、正二价锰盐与钴氰化钾即可。
所述的静置一段时间是指24-120小时。
所述的干燥指在温度为60-100℃烘箱干燥4-24小时。
所述的高温反应是指在600-1000℃反应2-12小时。
将以上所得Mn2Co2C@C与主体光催化剂石墨相氮化碳(g-C3N4)通过研磨得到复合光催化剂g-C3N4/Mn2Co2C@C。相比于g-C3N4,复合光催化剂g-C3N4/Mn2Co2C@C的光催化产氢活性得到了巨大的提高。
本发明的机理为:
本发明首先将可溶性的正二价钴盐(Co(NO3)2·6H2O)、正二价锰盐(Mn(NO3)2·4H2O)溶解在水中,然后加钴氰化钾(K3Co(CN)6),搅拌溶解完全后静置一段时间得到Co1Mn5[Co(CN)6]4钴锰普鲁士蓝沉淀,离心分离出沉淀,进一步干燥,然后在N2气氛下,将Co1Mn5[Co(CN)6]4高温热解,此过程中氰基(CN)碳化石墨化得到氮掺杂的碳,且氰基(CN)碳化过程产生的一氧化碳、二氧化碳、一氧化氮以及碳等还原性物质能够将钴锰还原碳化得到Mn2Co2C。因此,反应结束后即得目标产物氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)。将Mn2Co2C@C作为光催化剂石墨相氮化碳(g-C3N4)的助催化剂,通过研磨将Mn2Co2C@C负载在g-C3N4的表面,能够极大地提高g-C3N4的光催化分解水制氢活性。主体光催化剂g-C3N4可市购或通过以下方法制备:将尿素装在陶瓷坩埚中,盖上盖子,在马弗炉中550℃反应2小时得到目标产物。
相对于现有技术,本发明具有如下的优点及有益效果:
(1)本发明氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)可实现简单合成,能够快速放大工业化。
(2)本发明氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)结构新颖,作为光催化剂石墨相氮化碳(g-C3N4)的助催化剂能够极大地提高g-C3N4的光催化分解水制氢活性。
附图说明
图1为实施例1制备得到的Mn2Co2C@C的XRD图。
图2为实施例1制备得到的Mn2Co2C@C的SEM图。
图3为实施例1制备得到的Mn2Co2C@C的TEM图。
图4为实施例1制备得到的Mn2Co2C@C与g-C3N4结合后的复合光催化剂g-C3N4/Mn2Co2C@C的XRD图。
图5为实施例1制备得到的Mn2Co2C@C与g-C3N4结合后的复合光催化剂g-C3N4/Mn2Co2C@C的TEM图。
图6为实施例1制备得到的Mn2Co2C@C与g-C3N4结合后的复合光催化剂g-C3N4/Mn2Co2C@C的产氢总量随光照时间变化图。
图7为纯g-C3N4光催化剂的产氢总量随光照时间变化图。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例中所用试剂如无特殊说明均可从市场常规购得。
实施例中所述的光催化分解水水产氢测试方法如下:光催化分解水反应在Labsolar 6A光催化反应系统(北京泊菲莱)中进行,整个系统可以与真空泵联通。将20 mg光催化剂加入到装有85 mL去离子水/15 mL TEOA混合溶液的反应器中,超声分散3 min,搅拌均匀。将反应器与系统连接并密封好,整个系统用真空泵抽真空到2.0 kPa,反应器用15℃的冷凝水保持恒温,反应器中的悬浮液用磁力搅拌保持悬浮。反应器为顶照式,300 W氙灯作为光源,输入电压为220 V,电流为15 A,灯头可装配可见光滤光片(AM1.5)。反应开始后,通过自动进样系统每30 min或60 min取一个样,送入在线气相色谱仪检测反应生成的H2。
实施例1
本实施例氮掺杂碳包覆的纳米Mn2Co2C的制备方法,具体制备步骤如下:
将Co(NO3)2·6H2O(1.0 mmol, 291.0 mg)与Mn(NO3)2·4H2O(5.0 mmol, 1255.1 mg)溶于100 mL去离子水中,搅拌溶解。将K3Co(CN)6(4.0 mmol, 1329.3 mg)加入到上述溶液中,搅拌溶解,然后静置陈化24 h。沉淀经离心分离,于80℃干燥过夜得到钴锰普鲁士蓝。将干燥后的样品研磨均匀放入管式炉中,在N2气氛保护下,以5℃·min-1的升温速率升温到800℃,热解2小时反应结束后即得目标产物氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)。
本实施例所得Mn2Co2C@C的XRD图如图1所示,Mn2Co2C@C纳米颗粒的XRD图谱中显示三个强衍射峰,位于41.25°、47.95°与70.15°,分别对应于四方相Mn2Co2C(PDF#:65-1644)的(111)、(002)与(220)晶面。位于2θ=26.5°的特征峰对应氮掺杂碳的(002)晶面;说明成功合成了氮掺杂碳包覆的纳米Mn2Co2C。
本实施例所得氮掺杂碳包覆的Mn2Co2C的扫描电子显微镜图(SEM)如图2所示,Mn2Co2C@C是由不规则的纳米颗粒组成的,粒径为20-200 nm。
本实施例所得氮掺杂碳包覆的Mn2Co2C的投射电子显微镜图(TEM)如图3所示,Mn2Co2C@C具有明显的核壳结构,里面深色的核是Mn2Co2C,其表面的包覆层是氮掺杂碳。
将本实施例得到的Mn2Co2C@C与g-C3N4一起,使Mn2Co2C@C占二者总重的15%,机械研磨得到g-C3N4/Mn2Co2C@C复合光催化剂。g-C3N4/Mn2Co2C@C复合光催化剂的XRD图如图4所示,位于13.2°与27.5°的特征峰对应于四方相g-C3N4的(111)与(002)晶面。其它三个明显的特征峰,位于41.25°、47.95°与70.15°,分别对应于四方相Mn2Co2C(PDF#:65-1644)的(111)、(002)与(220)晶面。g-C3N4/Mn2Co2C@C复合光催化剂的TEM图如图5所示,可以明显观察到Mn2Co2C@C负载在g-C3N4的表面。以上结果说明成功制备得到了g-C3N4/Mn2Co2C@C复合光催化剂。
g-C3N4/Mn2Co2C@C复合光催化剂的产氢总量与光照时间关系如图6所示,其在3 h内的总产氢量为106.52 umol。如图7所示,在同样的条件下,纯g-C3N4光催化剂在3 h内的总产氢量为0.41 umol。因此,g-C3N4/Mn2Co2C@C的光催化产氢速率是g-C3N4的259.8倍,这个结果说明Mn2Co2C@C作为助催化剂可以有效的提高主体光催化剂g-C3N4的光催化析氢速率。
实施例2
本实施例氮掺杂碳包覆的纳米Mn2Co2C的制备方法,具体制备步骤如下:将Co(NO3)2·6H2O(1.0 mmol, 291.0 mg)与Mn(NO3)2·4H2O(5.0 mmol, 1255.1 mg)溶于100 mL去离子水中,搅拌溶解。将K3Co(CN)6(4.0 mmol, 1329.3 mg)加入到上述溶液中,搅拌溶解,然后静置陈化24 h。沉淀经离心分离,于80℃干燥过夜得到钴锰普鲁士蓝。将干燥后的样品研磨均匀放入管式炉中,在N2气氛保护下,以5℃·min-1的升温速率升温到700℃,热解4小时反应结束后即得目标产物氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)。
实施例3
本实施例氮掺杂碳包覆的纳米Mn2Co2C的制备方法,具体制备步骤如下:将Co(NO3)2·6H2O(1.0 mmol, 291.0 mg)与Mn(NO3)2·4H2O(5.0 mmol, 1255.1 mg)溶于100 mL去离子水中,搅拌溶解。将K3Co(CN)6(4.0 mmol, 1329.3 mg)加入到上述溶液中,搅拌溶解,然后静置陈化24 h。沉淀经离心分离,于80℃干燥过夜得到钴锰普鲁士蓝。将干燥后的样品研磨均匀放入管式炉中,在N2气氛保护下,以5℃·min-1的升温速率升温到900℃,热解2小时反应结束后即得目标产物氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)。
实施例4
本实施例氮掺杂碳包覆的纳米Mn2Co2C的制备方法,具体制备步骤如下:
将CoSO4·7H2O(1.0 mmol, 281.0 mg)与MnSO4(5.0 mmol, 755 mg)溶于100 mL去离子水中,搅拌溶解。将K3Co(CN)6(4.0 mmol, 1329.3 mg)加入到上述溶液中,搅拌溶解,然后静置陈化36h。沉淀经离心分离,于60℃干燥过夜得到钴锰普鲁士蓝。将干燥后的样品研磨均匀放入管式炉中,在N2气氛保护下,以5℃·min-1的升温速率升温到600℃,热解8小时反应结束后即得目标产物氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)。
实施例5
本实施例氮掺杂碳包覆的纳米Mn2Co2C的制备方法,具体制备步骤如下:
将(CH3COO)2Co(1.0 mmol, 177.0 mg)与(CH3COO)2Mn · 4H2O(5.0 mmol, 1225mg)溶于100 mL去离子水中,搅拌溶解。将K3Co(CN)6(4.0 mmol, 1329.3 mg)加入到上述溶液中,搅拌溶解,然后静置陈化48h。沉淀经离心分离,于100℃干燥过夜得到钴锰普鲁士蓝。将干燥后的样品研磨均匀放入管式炉中,在N2气氛保护下,以5℃·min-1的升温速率升温到1000℃,热解12小时反应结束后即得目标产物氮掺杂碳包覆的纳米Mn2Co2C(Mn2Co2C@C)。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种氮掺杂碳层包覆碳化钴锰复合材料,其特征在于,由包括以下步骤的方法制成:将可溶性正二价钴盐、正二价锰盐与钴氰化钾反应得到沉淀,沉淀在N2气氛保护下高温反应,即得。
2.根据权利要求1所述的氮掺杂碳层包覆碳化钴锰复合材料,其特征在于,由包括以下步骤的方法制成:
(1)制备钴锰普鲁士蓝:将可溶性的正二价钴盐、正二价锰盐溶解在水中,然后加入钴氰化钾,溶解完全后静置一段时间分离得到沉淀,所得沉淀进一步干燥得到钴锰普鲁士蓝;
(2)制备复合材料:将步骤(1)中所得钴锰普鲁士蓝研磨均匀,放入管式炉中在N2气氛保护下高温反应,反应结束后即得。
3.根据权利要求1所述的氮掺杂碳层包覆碳化钴锰复合材料,其特征在于:所述的可溶性正二价钴盐包括硝酸钴、硫酸钴和乙酸钴中的一种或多种。
4.根据权利要求1所述的氮掺杂碳层包覆碳化钴锰复合材料,其特征在于:所述的可溶性正二价锰盐包括硝酸锰、硫酸锰和乙酸锰中的一种或多种。
5. 根据权利要求1所述的氮掺杂碳层包覆碳化钴锰复合材料,其特征在于:所用可溶性正二价钴盐、正二价锰盐的摩尔比为1: 5。
6.根据权利要求1所述的氮掺杂碳层包覆碳化钴锰复合材料,其特征在于:所用可溶性正二价钴盐和正二价锰盐的摩尔总量与钴氰化钾的摩尔量之比为3:2。
7.根据权利要求1所述的氮掺杂碳层包覆碳化钴锰复合材料,其特征在于:所述的高温反应是指在600-1000℃反应2-12小时。
8.根据权利要求2所述的氮掺杂碳层包覆碳化钴锰复合材料,其特征在于:所述的静置一段时间是指24-120小时;所述的干燥指在温度为60-100℃烘箱干燥4-24小时。
9.权利要求1-8任一项所述氮掺杂碳层包覆碳化钴锰复合材料在光催化反应中的应用。
10.一种复合光催化剂,其特征在于:包括权利要求1-8任一项所述氮掺杂碳层包覆碳化钴锰复合材料和石墨相氮化碳g-C3N4。
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