CN111203243A - 一种硒化镍/石墨烯复合材料的制备及应用 - Google Patents
一种硒化镍/石墨烯复合材料的制备及应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000001509 sodium citrate Substances 0.000 claims abstract description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 5
- 239000011669 selenium Substances 0.000 claims description 78
- 238000004108 freeze drying Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229910052711 selenium Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 239000012286 potassium permanganate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
本发明公开了一种硒化镍/石墨烯复合材料的制备及应用,本发明制备方法以Se、NiCl2•6H2O、N2H4•H2O和柠檬酸钠作为前体制备硒化镍(Ni0.85Se),N2H4•H2O作为还原剂可以将Se还原为Se2‑,柠檬酸钠作为一种络合剂对反应有促进作用,通过在GO溶液热回流过程中加入N2H4•H2O作为还原剂,使得GO还原为RGO,Ni0.85Se和RGO通过水热反应形成复合材料Ni0.85Se/RGO。本发明制备的复合材料Ni0.85Se/RGO经过与导电性良好的RGO复合后,其导电性得到显著提高,用于电催化剂在电解水OER过程中表现出优异的电催化性能和良好的稳定性。
Description
技术领域
本发明属于复合材料技术领域,涉及一种硒化镍/石墨烯复合材料的制备,主要作为催化剂用于电解水析氧反应中。
背景技术
石墨烯是一种二维的碳纳米材料,已经广泛应用于超级电容器、电催化裂解水、锂离子电池、纳米材料以及储氢等领域。氧化石墨烯(GO)在表面和内部接枝有不同含氧官能团(如羟基、环氧基、烷氧基、羧基和羰基),这些含氧官能团可以增加石墨片层的层间距,并使得碳原子从sp2杂化转变为sp3杂化,使氧化石墨烯的亲水性提高,使得催化剂活性物种在石墨烯表面的均匀分散成为可能。氧化石墨烯和催化剂前驱体之间的氧化还原反应使得催化剂纳米颗粒可以在石墨烯的基底平面上自发沉积,从而提高催化剂颗粒的分散性,并且可以提供一个具有高的电子传导率的网状结构,以降低欧姆损耗。
硒化镍(Ni0.85Se)作为一种半导体材料由于其独特的电学及磁学性能、已经在光记录材料、太阳能电池、传感器、激光材料以及光纤等领域显示出了广阔的应用前景。近年来越来越多的人开始将其应用在电催化裂解水领域,由于其优异的电催化性能。但是纯硒化镍的导电性能还有待提高,因此将石墨烯和硒化镍复合在一起有望提高其导电性,从而提高其电催化裂解水的能力,使之作为一种电催化剂更好的应用于电解水领域。
发明内容
本发明的目的是提供一种硒化镍/石墨烯复合材料的制备方法。
本发明的另一个目的是提供上述硒化镍/石墨烯复合材料作为电催化剂用于电解水析氧反应中。
一、硒化镍/石墨烯复合材料的制备
本发明硒化镍/石墨烯复合材料的制备方法,包括以下工艺步骤:
(1)将NiCl2•6H2O和柠檬酸钠在去离子水中分散均匀得到NiCl2•6H2O和柠檬酸钠的混合液,将硒在N2H4•H2O中分散均匀得硒溶液,将NiCl2•6H2O和柠檬酸钠的混合液与硒溶液混合均匀,于120~160℃下水热反应8~12h,洗涤,冷冻干燥,得到硒化镍,标记为Ni0.85Se。其中,NiCl2•6H2O和柠檬酸钠的质量比1:1.4~1:1.8;硒与NiCl2•6H2O的质量比为1:2.5~1:2.8;硒溶液的质量浓度为23~48mg/mL。
(2)将氧化石墨烯于去离子水中分散均匀,加入N2H4•H2O作为还原剂,于85~95℃下回流反应5~8h,冷却,离心,洗涤,冷冻干燥得还原氧化石墨烯,标记为RGO。其中,氧化石墨与N2H4•H2O的质量体积比为15~30mg/mL;冷冻干燥时间为1~2天。
(3)将硒化镍和还原氧化石墨烯去离子水中分散均匀,于120~160℃下水热反应8~12h,洗涤,冷冻干燥,得到硒化镍/石墨烯复合材料,标记为Ni0.85Se/RGO。
其中,硒化镍和还原氧化石墨烯的质量比为1:1~1:2;冷冻干燥时间为1~2天,必须冷冻干燥而不是真空干燥,为的是让制得的硒化镍/石墨烯复合材料更疏松拥有更多孔,从而增加其比表面积,增加相应的活性位点,
二、硒化镍/石墨烯复合材料的表征
图1为RGO、Ni0.85Se和Ni0.85Se/RGO的红外光谱图。对于RGO,在3430cm-1附近有一个较宽、较强的吸收峰,归属于-OH的伸缩振动峰;在1630cm -1处的吸收峰归属于C-OH的弯曲振动吸收峰;在1110cm -1的峰为C-O-C的振动吸收峰。对于Ni0.85Se,在2295cm -1的峰为Ni-Se的振动吸收峰。Ni0.85Se/RGO既显示出RGO的特征峰又显示出Ni0.85Se的吸收峰(如图中黑色虚线所示),这表明Ni0.85Se/RGO的成功合成。
图2为RGO、Ni0.85Se和Ni0.85Se/RGO的X射线衍射谱图。由图可以看出RGO在26o有其特征峰,Ni0.85Se在33.4o、44.8o、50.8o、60.1o、62.1o和70.1o显示出特征峰,分别对应于(101),(102),(110),(103),(201)和(202)晶面。Ni0.85Se/RGO既在26o有RGO的特征峰,又在33.4o、44.8o、50.8o、60.1o、62.1o和70.1o显示出Ni0.85Se的特征峰,表明Ni0.85Se/RGO的成功合成,这与红外谱图得出的结果一致。
图3是Ni0.85Se(a)和Ni0.85Se/RGO(b)的扫描电镜图,从Ni0.85Se电镜图(图3a)可以看出,通过水热处理、冷冻干燥后,制备的Ni0.85Se呈花状。Ni0.85Se/RGO电镜图(图3b)显示Ni0.85Se的花状结构发生了一定的变化,这是因为引入RGO的缘故,从图中可以看出Ni0.85Se包裹在RGO表面,引入RGO的目的是提高其导电性,增加比表面积,从而提高催化剂的电催化性能。
三、硒化镍/石墨烯复合材料的电化学性能测试
工作电极的制备:将3.5~5.5mg Ni0.85Se、RGO、Ni0.85Se/RGO分别均匀分散于600μL水和400μL乙醇的混合溶液中,制成质量体积浓度为3.5~5.5mg/mL的分散液,将5μL该分散液滴涂到玻碳电极(GCE)上,制得工作电极Ni0.85Se/GCE,RGO/GCE和Ni0.85Se/RGO/GCE。
以饱和甘汞电极和Pt丝分别作为参比电极和对电极,以制备的Ni0.85Se/GCE,RGO/GCE和Ni0.85Se/RGO/GCE作为工作电极,设置电压范围0~0.8V,在扫描速率为0.1V/s下进行循环伏安扫描50圈,激活电极使电极达到信号稳定后,在扫描速率为0.005V/s进行线性伏安扫描法(LSV)。LSV曲线如图4所示,从图中可以看出,在电流密度为10mA/cm2时,复合材料Ni0.85Se/RGO的过电势最低,为352mV。三种工作电极在电流密度为10mA/cm2处的过电位大小关系为Ni0.85Se/RGO<Ni0.85Se<RGO,这表明复合材料Ni0.85Se/RGO具有最优异的电催化析氧性能。图5为Ni0.85Se、RGO和Ni0.85Se/RGO的电化学阻抗图,从图中可以看出单一的Ni0.85Se阻抗较大,经过与导电性良好的RGO复合后,其导电性得到显著提高。
采用计时电位法,在10mA/cm2电流密度下进行电解水析氧反应的稳定性测试,图6为Ni0.85Se/RGO的稳定性测试图。从图中可以看出随着时间的推移,电位基本不变,经过10h的稳定性测试,证明Ni0.85Se/RGO具有良好的稳定性。
综上所述,本发明制备方法以Se、NiCl2•6H2O、N2H4•H2O和柠檬酸钠作为前体制备硒化镍(Ni0.85Se)。N2H4•H2O作为还原剂可以将Se还原为Se2-,柠檬酸钠作为一种络合剂对反应有促进作用,通过在GO溶液热回流过程中加入N2H4•H2O,使得 GO还原为RGO,Ni0.85Se和RGO通过水热反应形成复合材料Ni0.85Se/RGO。电化学性能检测表明,经过与导电性良好的RGO复合后,Ni0.85Se/RGO导电性得到显著提高,用于电催化剂在电解水OER过程中表现出优异的电催化性能和良好的稳定性。
附图说明
图1为Ni0.85Se、RGO和Ni0.85Se/RGO的红外光谱图;
图2为Ni0.85Se、RGO和Ni0.85Se/RGO的X射线衍射谱图;
图3为Ni0.85Se(a)和Ni0.85Se/RGO(b)的扫描电镜图;
图4为Ni0.85Se、RGO和Ni0.85Se/RGO在1 M KOH溶液中电解水析氧反应的线性扫描曲线图;
图5为Ni0.85Se、RGO和Ni0.85Se/RGO的电化学阻抗图;
图6为Ni0.85Se/RGO的稳定性测试图。
具体实施方式
下面通过具体实施例对本发明硒化镍/石墨烯复合材料制备和性能作进一步说明。
实施例1
(1)将604mg NiCl2•6H2O和1g柠檬酸钠分散在25mL水中,磁力搅拌1h得到NiCl2•6H2O和柠檬酸钠的混合液。将237mg Se分散在10mL N2H4•H2O中,磁力搅拌0.5h得硒溶液。取25mLNiCl2•6H2O和柠檬酸钠的混合液加入到10mL 硒溶液中,磁力搅拌1h,然后将搅拌均匀的混合溶液超声1h,超声完毕后将混合溶液转移至含有聚四氟乙烯内衬的水热反应釜中,放入烘箱,在140℃下水热反应10h。反应完毕后离心洗涤3次,以除去残留的杂质,最后冷冻干燥2天制得硒化镍(Ni0.85Se);
(2)将磷片石墨放入坩埚,置于微波炉中,加热50s,制得膨胀石墨;将1g膨胀石墨放入500mL N-N二甲基甲酰胺(DMF)中,超声3天,用乙醇和水反复洗涤过滤,冷冻干燥,得到剥离的石墨;对剥离的石墨进行预氧化,将1g剥离的石墨粉、1.25g过硫酸钾、1.25g五氧化二磷放入100mL浓硫酸中在油浴锅中80℃回流12 h后加入200mL冰水稀释,最后过滤至中性,冷冻干燥2天。将1g预氧化石墨加入到90mL浓硫酸和50mL浓磷酸组成的混合酸液中,然后缓慢加入9g高锰酸钾,控制反应温度在5℃以下,以防止爆炸;待高锰酸钾溶解完全后,升温至50℃,搅拌12h;反应结束后,体系冷却到室温,分别加入250mL冰水和5mL质量分数30%的过氧化氢溶液至反应后液变为亮黄色,再滴入几滴盐酸反应过量的双氧水,离心,反复洗涤,冷冻干燥,得到氧化石墨烯(GO)。将90mg GO加入到25mL去离子水中超声0.5小时,超声完毕后,向溶液中加入5mL N2H4•H2O,在油浴锅中95℃下回流8h,待溶液冷却后离心洗涤,冷冻干燥2天得还原氧化石墨烯(RGO);
(3)将60mg Ni0.85Se和60mg RGO分散在30mL去离子水中,磁力搅拌2h,然后将搅拌均匀的混合溶液超声1h,超声完毕后将混合溶液转移至含有聚四氟乙烯内衬的水热反应釜中,放入烘箱,在140℃下水热反应10h。反应完毕后离心洗涤3次,以除去残留的杂质,最后冷冻干燥2天制得硒化镍/石墨烯复合材料(Ni0.85Se/RGO);
(4)Ni0.85Se/RGO的电化学性能测试:在电流密度为10mA/cm2,Ni0.85Se/RGO的过电位为352mV;电化学阻抗为15Ω。
实施例2
(1)同实施例1;
(2)同实施例1;
(3)将60mg Ni0.85Se和90mg RGO分散在30 mL去离子水中,磁力搅拌2h,然后将搅拌均匀的混合溶液超声1h,超声完毕后将混合溶液转移至含有聚四氟乙烯内衬的水热反应釜中,放入烘箱,在140℃下水热反应10h。反应完毕后离心洗涤3次,以除去残留的杂质,最后冷冻干燥2天制得硒化镍/石墨烯复合材料(Ni0.85Se/RGO);
(4)Ni0.85Se/RGO的电化学性能测试:在电流密度为10mA/cm2,Ni0.85Se/RGO的过电位为360mV;电化学阻抗为20Ω。
实施例3
(1)同实施例1;
(2)同实施例1;
(3)将60mg Ni0.85Se和120mg RGO分散在30mL去离子水中,磁力搅拌2小时,然后将搅拌均匀的混合溶液超声1h,超声完毕后将混合溶液转移至含有聚四氟乙烯内衬的水热反应釜中,放入烘箱,在140℃下水热反应10h。反应完毕后离心洗涤3次,以除去残留的杂质,最后冷冻干燥2天制得硒化镍/石墨烯复合材料(Ni0.85Se/RGO);
(4)Ni0.85Se/RGO的电化学性能测试:在电流密度为10mA/cm2,Ni0.85Se/RGO2的过电势为356mV;电化学阻抗为18Ω。
Claims (8)
1.一种硒化镍/石墨烯复合材料的制备方法,包括以下工艺步骤:
(1)将NiCl2•6H2O和柠檬酸钠在去离子水中分散均匀得到NiCl2•6H2O和柠檬酸钠的混合液,将硒在N2H4•H2O中分散均匀得硒溶液,将NiCl2•6H2O和柠檬酸钠的混合液与硒溶液混合均匀,于120~160℃下水热反应8~12h,洗涤,冷冻干燥,得到硒化镍,标记为Ni0.85Se;
(2)将氧化石墨烯于去离子水中分散均匀,加入N2H4•H2O作为还原剂,于85~95℃下回流反应5~8h,冷却,离心,洗涤,冷冻干燥得还原氧化石墨烯,标记为RGO;
(3)将硒化镍和还原氧化石墨烯在去离子水中分散均匀,于120~160℃下水热反应8~12h,洗涤,冷冻干燥,得到硒化镍/石墨烯复合材料,标记为Ni0.85Se/RGO。
2.如权利要求1一种硒化镍/石墨烯复合材料的制备方法,其特征在于:步骤(1)中,NiCl2•6H2O和柠檬酸钠的质量比1:1.4~1:1.8。
3.如权利要求1一种硒化镍/石墨烯复合材料的制备方法,其特征在于:步骤(1)中,硒与NiCl2•6H2O的质量比为1:2.5~1:2.8;硒溶液的质量浓度为23~48mg/mL。
4.如权利要求1一种硒化镍/石墨烯复合材料的制备方法,其特征在于:步骤(2)中,氧化石墨烯与N2H4•H2O的质量体积比为15~30mg/mL。
5.如权利要求1一种硒化镍/石墨烯复合材料的制备方法,其特征在于:步骤(2)中,冷冻干燥时间为1~2天。
6.如权利要求1一种硒化镍/石墨烯复合材料的制备方法,其特征在于:步骤(3)中,硒化镍和还原氧化石墨烯的质量比为1:1~1:2。
7.如权利要求1一种硒化镍/石墨烯复合材料的制备方法,其特征在于:步骤(3)中,冷冻干燥时间为1~2天。
8.如权利要求1所述方法制备的硒化镍/石墨烯复合材料作为电催化剂用于电解水析氧反应中。
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