CN113694952B - 一种含硫空位NiS量子点/S,N,O共掺杂碳电极材料及其制备方法 - Google Patents
一种含硫空位NiS量子点/S,N,O共掺杂碳电极材料及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 112
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 97
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 67
- 239000002096 quantum dot Substances 0.000 title claims abstract description 57
- 239000007772 electrode material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004744 fabric Substances 0.000 claims abstract description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011593 sulfur Substances 0.000 claims abstract description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 26
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 17
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011888 foil Substances 0.000 claims abstract description 13
- LTPUNSOVDZWNSX-UHFFFAOYSA-N methylthiourea pyrimidine Chemical compound N1=CN=CC=C1.CNC(=S)N LTPUNSOVDZWNSX-UHFFFAOYSA-N 0.000 claims abstract description 13
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008878 coupling Effects 0.000 claims abstract description 7
- 238000010168 coupling process Methods 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 238000004073 vulcanization Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000006056 electrooxidation reaction Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 25
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 8
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
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- 239000011247 coating layer Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DVVGBNZLQNDSPA-UHFFFAOYSA-N 3,6,11-trioxabicyclo[6.2.1]undeca-1(10),8-diene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1O2 DVVGBNZLQNDSPA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 150000001721 carbon Chemical class 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- -1 transition metal chalcogenides Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
本发明公开了一种含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料及其制备方法,含有硫空位的NiS量子点均匀镶嵌在生长于碳布上的S,N,O共掺杂碳网络中,形成碳布自支撑的复合电极材料。将NiCl2·6H2O、甲基硫脲嘧啶、乙二醇混合,加热搅拌形成均相液体,均匀地滴涂在碳布表面,放入瓷舟中,将用铝箔包好的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,400‑600℃保温0.5‑5h,通过一步完成的热解、硫化与耦合协同反应得到所述电极材料,该电极材料用于5‑羟甲基糠醛电氧化制备2,5‑呋喃二甲酸和水的电还原制氢,都有很高的电催化活性。
Description
技术领域
本发明属于电催化材料与技术领域,涉及一种含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的制备方法,具体地说,是涉及一种具有硫空位的NiS量子点均匀镶嵌在生长于碳布上的S,N,O共掺杂碳网络中所形成的复合电极材料的制备方法,进一步地,涉及一种用于5-羟甲基糠醛电氧化制备2,5-呋喃二甲酸和水的电还原制氢的双功能高活性电极材料的制备方法。
背景技术
电催化分解水制氢作为一种环保的制氢方法受到了全世界的关注。然而,在水分解反应中,由于产氧反应(OER)的动力学非常缓慢,需要高过电位来克服高能垒,导致能量转换效率相对较低。此外,OER产氧的应用价值不大。而具有热力学上更有利于生物质氧化的电催化氧化反应更具有吸引力,可将生物质分子转化为高附加值精细化学品。其中,2,5-呋喃二甲酸(FDCA)是生物基聚合物单体最重要的产品之一,FDCA还可以用作石油衍生的对苯二甲酸的有前途的替代品,用于生产聚(2,5-呋喃二甲酸乙二醇酯)。HMF的选择性氧化被认为是生产FDCA的诱人途径。最常用的策略是通过均相和/或非均相催化的化学转化。但是,通常需要高压和高温氧等苛刻的条件,与化学催化相比,电化学催化氧化可在室温和常压下将HMF转化为FDCA而得到了广泛的关注。迄今为止,Pd,Au和Pt基贵金属催化剂被认为是HMF氧化生产FDCA的最常用的催化剂,但由于其价格昂贵和储量低,极大的限制了其实际应用。
近年来,人们致力于非贵金属催化剂的研究,过渡金属的Ni,Co,Cu和Mn化合物催化剂显示出HMF催化氧化的潜力。硫化镍是一类高活性的过渡金属硫属化合物,然而,由于硫化镍固有电子电导率相对较低,需要高的过电势,并且硫化镍稳定性较差。迫切需要探索新的设计策略开发具有充分暴露的活性位点、高导电性和高稳定性的独特结构以提高硫化镍生物质氧化性能和HER性能。
另外,电催化反应催化材料电极的制备,传统方法通常是采用加入胶粘剂和导电石墨与活性电极材料做成糊状涂抹到电极集流体上,胶黏剂的使用使得活性电极材料的性能难以充分发挥作用。为解决这一问题,利用碳布作为电极集流体,使硫化镍电极材料直接生长在碳布骨架上,可以使硫化镍电极材料的电化学性能通过协同作用而大大提高。
发明内容:
本发明针对现有技术中制备的NiS/C催化剂电极过程复杂繁琐、需要多步合成,难以实现紧密的界面耦合,电催化效率低,长期稳定性差等缺点,提出了一种绿色高效的一步反应策略,通过一步热解、硫化与耦合协同反应,制备了具有硫空位的NiS量子点均匀镶嵌在生长于碳布上的S,N,O共掺杂碳网络中的复合电极材料,从而大大提高电化学活性和稳定性。嵌入在碳网络结构中的具有硫空位的NiS量子点既可以保留硫化镍的活性中心,又可以保护活性位点,提高其耐久性,还可以有效改善电子/电荷转移效率。该复合电极材料对HMF氧化转化为FDCA具有高活性和选择性,同时对水还原产氢反应(HER)具有高活性。
一种含硫空位NiS量子点/S,N,O共掺杂碳电极材料及其制备方法,其特征在于,含有硫空位的NiS量子点均匀镶嵌在生长于碳布上的S,N,O共掺杂碳网络中,形成碳布自支撑的复合电极材料,所述电极材料用于5-羟甲基糠醛电氧化制备2,5-呋喃二甲酸和水的电还原制氢,都有很高的电催化活性,通过一步完成的热解、硫化与耦合协同反应来制备,具体包括下述步骤:
(1)将0.001-0.1mol NiCl2·6H2O、0.001-0.2mol甲基硫脲嘧啶、0.001-0.5mol乙二醇混合,在40-90℃的油浴锅中加热搅拌0.1-2h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以2-10℃/min的速度加热至400-600℃,保温0.5-5h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
本发明的优点在于:该方法工艺简单,通过一步热解、硫化与耦合协同反应,制备了具有硫空位的NiS量子点均匀镶嵌在互连的S,N,O共掺杂碳的网络结构中的复合材料。具有氧空位的NiS量子点与S,N,O共掺杂碳的网络结构形成分子水平的偶联界面,提高NiS催化剂耐腐蚀,耐高温,耐酸碱性,碳布自支撑的复合电极材料有利于长期的电催化稳定性和有效的界面电荷转移。同时,碳布和S,N,O共掺杂碳的网络结构充当高导电性骨架,表面分散的NiS量子点能够提供更多的活性位点,促使电子快速迁移到表面吸附更多的H+生成H2,从而提高了析氢性能;硫空位的引入有利于电荷转移。
本发明所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的电催化效率高,对于电催化分解水制氢和电催化氧化有机物都有很好的电催化活性。
附图说明
图1为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的XRD谱图。
图2为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的拉曼图谱。
图3为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的不同放大倍数的SEM照片。
图4为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的TEM照片(a)和HRTEM(b)照片。
图5为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的STEM图像和STEM-Mapping图像。
图6为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的ESR谱图。
图7为利用本发明实施例一、对比例所制备电极材料及碳布电催化产氢性能LSV曲线。
图8为实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料电催化析氢的循环稳定性。
图9为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料用于电催化氧化5-羟甲基糠醛(HMF)的转化率曲线。
具体实施方式:
下面通过实施例对本发明作进一步详细说明:
实施例一:
(1)将0.005mol NiCl2·6H2O、0.0075mol甲基硫脲嘧啶、0.01mol乙二醇混合,在70℃的油浴锅中加热搅拌0.4h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以5℃/min的速度加热至550℃,保温4h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
实施例二:
(1)将0.005mol NiCl2·6H2O、0.0075mmol甲基硫脲嘧啶、0.02mmol乙二醇混合,在70℃的油浴锅中加热搅拌0.4h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以5℃/min的速度加热至550℃,保温4h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
实施例三:
(1)将0.005mmol NiCl2·6H2O、0.0075mmol甲基硫脲嘧啶、0.005mol乙二醇混合,在70℃的油浴锅中加热搅拌0.4h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以5℃/min的速度加热至550℃,保温4h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
实施例四:
(1)将0.01mmol NiCl2·6H2O、0.05mmol甲基硫脲嘧啶、0.01mol乙二醇混合,在70℃的油浴锅中加热搅拌1h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以2℃/min的速度加热至450℃,保温2h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
实施例五:
(1)将0.05mmol NiCl2·6H2O、0.1mmol甲基硫脲嘧啶、0.05mmol乙二醇混合,在70℃的油浴锅中加热搅拌1h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以10℃/min的速度加热至600℃,保温2h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
实施例六:
(1)将0.05mmol NiCl2·6H2O、0.075mmol甲基硫脲嘧啶、0.04mmol乙二醇混合,在60℃的油浴锅中加热搅拌0.2h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以10℃/min的速度加热至500℃,保温3h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
实施例七:
(1)将0.05mmol NiCl2·6H2O、0.15mmol甲基硫脲嘧啶、0.3mmol乙二醇混合,在80℃的油浴锅中加热搅拌1h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以2℃/min的速度加热至600℃,保温4h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
实施例八:
(1)将0.05mmol NiCl2·6H2O、0.20mmol甲基硫脲嘧啶、0.1mmol乙二醇混合,在60℃的油浴锅中加热搅拌2h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以10℃/min的速度加热至600℃,保温3h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
对比例一:
(1)将0.005mol NiCl2·6H2O、0.0075mol甲基硫脲嘧啶、0.01mol乙二醇混合,在70℃的油浴锅中加热搅拌0.4h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,再将瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以5℃/min的速度加热至550℃,保温4h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
对比例二:
(1)将0.005mol NiCl2·6H2O溶于5ml去离子水中得到溶液A、0.005mol硫化钠溶于5ml去离子
水中得到溶液B;
(2)将溶液A和溶液B混合,生成黑色NiS沉淀,经水洗和醇洗干燥后,得到NiS。
对比例三:
(1)将0.0075mol甲基硫脲嘧啶、0.01mol乙二醇,在70℃的油浴锅中搅拌0.4h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以5℃/min的速度加热至550℃,保温4h,得到在碳布上生长的S,N,O共掺杂碳电极材料。
图1为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的XRD谱图。由图可以看出,除了在25-29°左右有一个鼓包,是无定形碳的衍射峰外,所有样品均与NiS的标准衍射峰一致(JPCDS,77-1624),说明所得样品为含有NiS的碳复合材料。
图2为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的拉曼图谱。由图可以看出,样品在1354cm-1和1583cm-1处有两个典型的特征峰,分别与无定形碳的D峰和G峰匹配,进一步确认样品中碳材料的存在。
图3为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的不同放大倍数的SEM照片。从图3a可以看出,碳布的碳纤维上沉积了包覆层。经放大后由SEM照片图3b可以清晰的观察到这层包覆层是由网络结构的复合材料组成。
图4为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的TEM照片(a)和HRTEM(b)照片。从图4a TEM照片可以看出,NiS量子点均匀点缀在互连的S,N,O共掺杂碳的网络结构中,碳布和S,N,O共掺杂碳的网络结构充当高导电性骨架,表面镶嵌的高分散NiS量子点能够提供更多的活性位点,促使电子快速迁移到表面吸附更多的H+生成H2,有利于水还原产氢性能和生物质电氧化性能的提高。图4b HRTEM照片,可以看出,NiS量子点镶嵌在S,N,O共掺杂碳的表面,大小在2-6nm左右,还可以清晰的观察到NiS量子点与S,N,O共掺杂碳之间紧密的异质界面,NiS量子点的晶面间距是0.198nm对应于NiS的(102)晶面,进一步说明复合电极材料是由NiS量子点/S,N,O共掺杂碳网络结构复合而成。
图5为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的STEM图像和STEM-Mapping图像。从ADF-STEM图像可以清楚地看出均匀分布的NiS量子点,Ni元素和S元素的STEM-Mapping衬度较弱,与其量子点分布的特征一致,C元素的分布与样品的ADF-STEM图像一致。STEM-Mapping图像进一步说明电极材料镶嵌有NiS量子点的S,N,O共掺杂碳网络复合材料。
图6为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料的ESR谱图。从图可以看出,位于g=2.002处有一对强峰,这是硫空位的特征峰,表明NiS量子点/S,N,O共掺杂碳网络电极材料中存在硫空位而产生的未配对电子。
图7为利用本发明实施例一、对比例所制备电极材料及碳布电催化产氢性能LSV曲线。电催化水还原产氢性能在1mol L-1KOH溶液中,以所制备的电极材料为工作电极,采用标准三电极体系记录线性扫描伏安(LSV)曲线。从图7中可看出,实施例一复合电极材料在10mA cm-2电流下的过电位是63mV,远低于对比例一不包裹铝箔所制备NiS量子点/掺杂碳网络电极材料、对比例二制备的NiS纳米材料和对比例三制备的S,N,O共掺杂碳网络结构电极材料在10mA cm-2电流下的过电位193mV和307mV,说明本发明实施例一所述方法制备的在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合电极材料的HER活性远高于对比例所制备电极材料和所用碳布,在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合电极材料能够大大地提高复合硫化镍的电催化活性。
图8为实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料电催化析氢的循环稳定性。从图中可以看出,反应24h后,在碱性条件、不通电流密度下的产氢性能基本保持不变,说明在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料用于碱性条件下的电催化析氢具有很好的稳定性。
图9为利用本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料用于电催化氧化5-羟甲基糠醛(HMF)制备2,5-呋喃二甲酸(FDCA)的转化率曲线。电催化氧化HMF制备FDCA过程中,采用高效液相色谱分析体系中HMF与氧化产物FDCA和5-羟甲基-2-呋喃甲酸(HMFCA)的浓度随时间变化情况,可以看出,随着HMF浓度的减小,FDCA的产率逐渐升高,180min后FDCA的浓度达到最大值,接近100%,而其他的氧化产物如HMFCA的浓度一直很小且没有明显变化,说明实施例一复合电极材料用于电催化氧化HMF制备FDCA具有很高的选择性。
进一步将本发明实施例一所述方法制备的含硫空位NiS量子点/S,N,O共掺杂碳网络电极材料用于水溶液中常见有机染料的电催化氧化降解,结果表明本发明所制备的复合电极材料对于常见有机染料的电催化降解也有很好的电催化活性,可以用于有机废水的电催化氧化处理。
上述实施例是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,未背离本发明的原理与工艺过程下所作的其它任何改变、替代、简化等,均为等效的置换,都应包含在本发明的保护范围之内。
Claims (1)
1.一种含硫空位NiS量子点/S,N,O共掺杂碳电极材料的制备方法,其特征在于,含有硫空位的NiS量子点均匀镶嵌在生长于碳布上的S,N,O共掺杂碳网络中,形成碳布自支撑的复合电极材料,所述电极材料用于5-羟甲基糠醛电氧化制备2,5-呋喃二甲酸和水的电还原制氢,通过一步完成的热解、硫化与耦合协同反应来制备,具体包括下述步骤:
(1)将0.001-0.1mol NiCl2·6H2O、0.001-0.2mol甲基硫脲嘧啶、0.001-0.5mol乙二醇混合,在40-90℃的油浴锅中加热搅拌0.1-2h,形成均相液体;
(2)将步骤(1)所得均相液体,均匀地滴涂在碳布表面,将所得碳布放入瓷舟中,用铝箔包裹瓷舟,将包裹的瓷舟放入管式炉中,用高纯氮气置换空气,在密闭条件下,以2-10℃/min的速度加热至400-600℃,保温0.5-5h,得到在碳布上生长的含硫空位NiS量子点/S,N,O共掺杂碳网络结构复合材料。
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