CN109663608A - 一种碳-钴钼双金属磷化物复合材料及其制备方法 - Google Patents
一种碳-钴钼双金属磷化物复合材料及其制备方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IOXWITJCAFZJQX-UHFFFAOYSA-N [C].[Co].[Mo] Chemical compound [C].[Co].[Mo] IOXWITJCAFZJQX-UHFFFAOYSA-N 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
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- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 150000002894 organic compounds Chemical class 0.000 claims description 17
- 229910017263 Mo—C Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 235000013339 cereals Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
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- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
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- 150000001875 compounds Chemical class 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 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
- 229910020679 Co—K Inorganic materials 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007740 vapor deposition 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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Abstract
一种碳‑钴钼双金属磷化物复合材料及其制备方法,该复合材料由具有十二面体结构的碳骨架以及均匀镶嵌于其中的MoP、CoP、以及CoMoP2纳米颗粒组成。其中十二面体结构碳骨架的有效保持,纳米双金属磷化物颗粒均匀镶嵌于碳基体中,不仅可以防止纳米颗粒的团聚与脱落,增强催化剂的稳定性,还可以发挥碳基体的高导电性与纳米双金属磷化物颗粒之间的协同作用,进一步增强磷化物的催化活性;碳骨架可有效提高整体催化剂材料的导电性,从而进一步提高其催化性能;双金属磷化物各相之间的协同作用对于提高电化学催化性能具有重要的作用;纳米双金属磷化物均匀镶嵌于碳基体中,可以防止纳米颗粒的团聚与脱落,增强催化剂的稳定性,且该复合材料在碱性环境中也具有优异的电化学析氢性能。
Description
技术领域
本发明涉及一种碳-钴钼双金属磷化物复合材料Co-Mo-P-C及其制备方法,以及该复合材料在电催化制氢技术领域的应用。
背景技术
催化制氢具有效率高、能耗低以及环境友好等优点,是极具应用前景的制氢技术。但是由于目前存在严重的阴极极化问题,大大增加了催化制氢技术的能耗,从而提高了制氢成本。Pt等贵金属以及它们的合金具有最好的电催化氢气析出性能,但是它们的成本高,难以大规模应用。发展高性能低成本的非贵金属催化剂对推动电催化制氢技术的应用具有重要意义。
过渡金属(Fe、Co、Ni、Mn)磷化物具有成本低廉,析氢催化活性优异以及制备方式多样等优点,近年得到迅速发展。但是目前所制备的金属磷化物在析氢过程中稳定性不好。
双金属磷化物由于不同元素之间的协同效应,有着比单金属磷化物更优异的性能,这使其成为了替代贵金属电催化剂的理想材料。Ting Zhang等(The Hybrids ofCobalt/Iron Phosphides Derived from Bimetal-Organic Frameworks as HighlyEfficient Electrocatalysts for Oxygen Evolution Reaction[J].ACS AppliedMaterials&Interfaces,2016,9(1),1-6)合成钴铁金属有机化合物CoFe-MOFs,然后将干燥好的CoFe-MOFs与NaH2PO2在管式炉中反应制得双金属Co-Fe-P,利用同样方法合成的FeP2、CoP做对比发现Co-Fe-P比FeP2、CoP的活性都要好,证明了协同作用的存在使Co-Fe-P的活性增强。Hanfeng Liang等(.Plasma-Assisted Synthesis of NiCoP for EfficientOverall Water Splitting[J].Nano Letters,2016,16(12):7718-7725)利用溶剂热法将镍钴氢氧化物前驱体生长在泡沫镍的表面,再利用等离子辅助的方法,将镍钴的氢氧化物转变成了NiCoP,合成的NiCoP在HER催化反应中展示了优异的活性。碱性介质中10mA·cm-2时对应的过电势仅32mV,利用密度泛函理论计算发现,水分子在NiCoP(0001)晶面上的吸附比在Pt(111)晶面上的吸附更强烈,揭示了NiCoP在碱性环境中具有较好HER催化活性的原因。
发明内容
本发明的目的在于提供一种碳复合的双金属磷化物Co-Mo-P-C,该复合材料由具有十二面体结构的碳骨架以及均匀镶嵌于其中的MoP、CoP、以及CoMoP2纳米颗粒组成。
双金属磷化物复核材料的形貌、尺寸、组成对其电催化活性有显著的影响,(1)本发明在具有十二面体结构的碳骨架基体上制备获得了Co-Mo-P-C复合材料,十二面体结构碳骨架的有效保持,纳米双金属磷化物颗粒均匀镶嵌于碳基体中,不仅可以防止纳米颗粒的团聚与脱落,增强催化剂的稳定性,还可以发挥碳基体的高导电性与纳米双金属磷化物颗粒之间的协同作用,进一步增强磷化物的催化活性;(2)碳骨架可有效提高整体催化剂材料的导电性,从而进一步提高其催化性能;(3)双金属磷化物各相之间的协同作用对于提高电化学催化性能具有重要的作用;(4)纳米双金属磷化物均匀镶嵌于碳基体中,可以防止纳米颗粒的团聚与脱落,增强催化剂的稳定性;(5)碳复合的双金属磷化物Co-Mo-P-C在碱性环境中具有优异的电化学析氢性能。
本发明的一种双金属磷化物复合材料的制备方法是按下列步骤进行:
按照以下步骤制备:
1)按照质量比1∶1-3称取Co(NO3)2·6H2O和2-甲基咪唑,然后分别将其溶于甲醇中,待搅拌溶解后,将2-甲基咪唑溶液倒入Co(NO3)2溶液中搅拌,停止搅拌后在室温下老化24h,之后将产物离心分离并清洗、干燥,得到具有十二面体结构的Co基有机化合物;
2)将MoO3与步骤1)得到的Co基有机化合物置于石英舟中放入管式电阻炉,之后将其置于氩气氛围中升温至700-900℃,并保温1-4h,从而得到含有MoO2、Mo2C与Co单质的Co-Mo-C复合材料;
3)将上述Mo-Co-C复合材料与磷酸氢二铵分别按照1-3∶5-8的质量比置于磁舟的两端,将磁舟放置于管式炉内,在氢气气氛下升温至720-950℃并保温1-3h进行磷化,待冷却至室温后得到碳复合双金属磷化物材料Co-Mo-P-C。
其中步骤1)中所述清洗干燥为采用甲醇洗涤3次,然后在60℃下真空干燥8h。
步骤2)中MoO3的加入量为120mg,Co基有机化合物的加入量40mg,并在氩气氛围中以5℃/min的升温速率,升温至800℃,并保温2h。
本发明的方法有如下特点:
(1)通过前驱体Co基有机化合物碳化后获得了含有Co单质的十二面体多孔碳基体材料,并确保活性物质颗粒均匀分散在多孔碳基体中。
(2)通过将MoO3与Co基有机化合物共同加热,MoO3高温升华引入Mo元素,在煅烧过程中,利用钴金属对氧的化学吸附,气化的MoO3会被吸附在Co单质周围再被碳还原,得到高分散度于碳基体的材料Co-Mo-C复合材料,随后进行磷化,制备均匀镶嵌于碳基体的碳复合双金属磷化物材料Co-Mo-P-C。Co与Mo元素均匀镶嵌于碳基体内部,阻止颗粒团聚,达到提高比表面积增强催化活性的目的。
附图说明
图1为实施例1步骤1)具有十二面体结构的Co基有机化合物的SEM形貌图。
图2为实施例1步骤2)所得Co-Mo-C复合材料的XRD图。
图3为实施例1步骤3)所得Co-Mo-C复合材料的SEM图。
图4为实施例1所得的纳米级Co-Mo-P-C双金属磷化物的XRD图。
图5为实施例1所得的纳米级Co-Mo-P-C双金属磷化物SEM图。
图6为实施例1所得的纳米级Co-Mo-P-C双金属磷化物HR-TEM图谱。
图7为实施例1所得Co-Mo-P-C,Co-Mo-C与对比例Co-C,Co-P-C,Mo-P以及商业Pt-C催化剂在0.5M H2SO4溶液中电解水析氢的LSV图谱。
图8为实施例1所得Co-Mo-P-C与Co-Mo-C,对比例Co-C,对比例Co-P-C,对比例Mo-P以及商业Pt-C催化剂的在1M KOH溶液中电解水析氢的LSV图谱。
图9为实施例1所得Co-Mo-P-C在0.5M的H2SO4溶液中循环伏安扫描的第1圈和第1000圈的极化曲线。
图10为实施例1所得Co-Mo-P-C在1M的KOH溶液中循环伏安扫描的第1圈和第1000圈的极化曲线。
具体实施方式
实施例1
(1)称取0.996gCo(NO3)2·6H2O和1.312g 2-甲基咪唑,分别溶于100ml甲醇中,搅拌10分钟,待搅拌溶解后,将2-甲基咪唑溶液迅速倒入Co(NO3)2溶液中,继续搅拌10min,停止搅拌后室温下老化24h,之后将产物离心分离,用甲醇洗涤3次,最后60℃真空干燥8h,所得产物即为多面体形金属有机化合物Co基有机化合物,产物呈蓝紫色,形状为菱形十二面体形。
(2)将120mg MoO3与40mgCo基有机化合物置于石英舟中放入管式电阻炉,在氩气氛围下以5℃/min的升温速率由室温升至目标温度800℃,并恒定2h,通过MoO3加热升华将Mo元素引入有钴金属单质的十二面体多孔碳复合材料Co-C中,制备得到含有MoO2、Mo2C与Co单质的Co-Mo-C复合材料。
(3)将上述Co-Mo-C复合材料与磷酸氢二铵分别按照1∶5的质量比置于磁舟的两端,将磁舟放置于管式炉内,在氢气气氛下升温至850℃并保温2h进行磷化,待冷却至室温后得到碳复合双金属磷化物材料Co-Mo-P-C。
实施例2
(1)称取1g的Co(NO3)2·6H2O和3g的2-甲基咪唑,分别溶于100ml甲醇中,搅拌10分钟,待搅拌溶解后,将2-甲基咪唑溶液迅速倒入Co(NO3)2溶液中,继续搅拌20min,停止搅拌后室温下老化14h,之后将产物离心分离,用甲醇洗涤3次,最后60℃真空干燥12h,所得产物即为多面体形金属有机化合物Co基有机化合物,产物呈蓝紫色,形状为菱形十二面体形。
(2)将150mg MoO3与60mgCo基有机化合物置于石英舟中放入管式电阻炉,在氩气氛围下以5℃/min的升温速率由室温升至目标温度750℃,并恒定4h,通过MoO3加热升华将Mo元素引入有钴金属单质的十二面体多孔碳复合材料Co-C中,制备得到含有MoO2、Mo2C与Co单质的Co-Mo-C复合材料。
(3)将上述Co-Mo-C复合材料与次磷酸钠分别按照1∶6的质量比置于磁舟的两端,将磁舟放置于管式炉内,在氩气氛下升温至750℃并保温4h,进行磷化,待冷却至室温后得到碳复合双金属磷化物材料Co-Mo-P-C。
对比例1:
将采用实施例1所述步骤(1)、(2)制备得到的含有钴金属单质的十二面体多孔碳复合材料Co-C置于石英舟中放入管式电阻炉,在氩气氛围下以5℃/min的升温速率由室温升至目标温度800℃,并恒定2h,制得含有Co单质的多孔碳,得到材料表示为Co-C。
对比例2:
然后将40mg的Co-C材料与(NH4)2HPO4按照1∶5的质量比分别置于磁舟的两端,将磁舟放置于管式炉内(NH4)2HPO4置于气流的上游,在氢气氛围下以5℃/min的升温速率由室温升至目标温度850℃恒定2h,进行磷化,得到材料表示为Co-P-C。
对比例3:
将MoO3与(NH4)2HPO4按照1∶5的质量比分别置于磁舟的两端,将磁舟放置于管式炉内(NH4)2HPO4置于气流的上游,在氢气氛围下以5℃/min的升温速率由室温升至目标温度850℃恒定2h,进行磷化,得到材料表示为Mo-P。
性能测试
对上述实施例1获得的碳复合双金属磷化物材料Co-Mo-P-C与对比例1、2、3得到的材料进行表征和测试。粉末X射线衍射(XRD)图谱利用布鲁克D8Advance测试仪,管电流40mA,管电压40kV,使用Cu-Kα射线与Co-Kα射线测试取得。扫描电子显微镜(SEM)图利用Hitachi SU8020采集。高分辨TEM(HR-TEM)图利用JEM 1200EX采集。电催化活性利用法国Bio-Logic公司的SP-50型电化学工作站测定。电解水析氢性能测试以0.5mol L-1 H2SO4与1mol L-1 KOH作为电解液,以10mV S-1的速率进行线性扫描伏安法测试。
图1为实施例1步骤1)具有十二面体结构的Co基有机化合物的SEM形貌图,由图中可见具有十二面体结构的Co基有机化合物具有较为均匀规整的形貌,展现了棱角分明的十二面体结构,平均粒径在600nm左右。
图2为实施例1步骤2)所得Co-Mo-C复合材料的XRD图,从图中可以看出材料由三种物相组成,一种是面心立方结构的单质钴,一种是单斜相MoO2,一种是六方相Mo2C。
图3为实施例1所得的纳米级Co-Mo-P-C双金属磷化物的SEM图。从图中可以看出,大部分颗粒的宏观形貌保持了Co基有机化合物的十二面体,没有发生任何结构坍塌。
图4为实施例1所得的纳米级Co-Mo-P-C双金属磷化物的XRD图。由图中可以看出,所述Co-Mo-P-C材料中同时具有MoP、CoP与CoMoP2的衍射峰。
图5为实施例1所得的纳米级Co-Mo-P-C双金属磷化物的SEM图。由图中可以看出,Co-Mo-P-C材料继承Co基有机化合物颗粒的十二面体形貌,但经过高温气相沉积及高温磷化后,材料表面变得粗糙并伴有颗粒的团聚。
图6为实施例1所得的纳米级Co-Mo-P-C双金属磷化物HR-TEM图。由图中可以看出Co-Mo-P-C材料是由直径为20nm-100nm颗粒组成,双金属磷化物颗粒镶嵌于碳骨架中,并且可以看到大部分颗粒具有明显的核壳结构,这不仅可以防止纳米颗粒的团聚与脱落,增强催化剂的稳定性,还可以发挥碳基体的高导电性与纳米双金属磷化物颗粒之间的协同作用,进一步增强磷化物的催化活性。在结构核心处有结晶度良好的CoP晶体,晶体有清晰的晶格条纹,并且CoP晶体周围分布着MoP晶体与少量的CoMoP2晶体。
图7为实施例1所得Co-Mo-P-C与Co-Mo-C,对比例1所得Co-C,对比例2所得Co-P-C,对比例3所得Mo-P以及商业Pt-C催化剂在0.5M H2SO4溶液中电解水析氢的LSV图谱。可以看出,在酸性溶液中,除了商业铂碳,活性最好的是Co-Mo-P-C,其在电流密度为10mAcm-2时,对应的过电势为148mV。双金属磷化物Co-Mo-P-C较单一的Mo-P或者Co-P-C的HER催化活性要高,Co-Mo-P-C的协同效应使其活性得到提高。
图8为实施例1所得Co-Mo-P-C与Co-Mo-C,对比例1所得Co-C,对比例2所得Co-P-C,对比例3所得Mo-P以及商业Pt-C催化剂的在1M的KOH溶液中电解水析氢的LSV图谱。可以看出,在碱性溶液中,除了商业铂碳,活性最好的是Co-Mo-P-C,其在电流密度为10mAcm-2时,对应的过电势为159mV。在碱性溶液中,双金属磷化物Co-Mo-P-C较单一的Mo-P或者Co-P-C的HER催化活性有非常明显的提高。
图9为实施例1所得Co-Mo-P-C在0.5M的H2SO4溶液中循环伏安扫描的第1圈和第1000圈的极化曲线。比较第一圈与最后一圈的中起始电势跟过电势,发现差别非常小,两者的极化曲线几乎完全重合,这表明材料的活性变化较小,说明Co-Mo-P-C在酸性溶液中具有很好的电解水催化稳定性。
图10为实施例1所得Co-Mo-P-C在1M KOH溶液中循环伏安扫描的第1圈和第1000圈的极化曲线。经过1000次循环之后材料Co-Mo-P-C的活性只有很小幅度的下降,表明该材料在在碱性溶液中也具有较好的电解水催化稳定性。
Claims (8)
1.一种碳-钴钼双金属磷化物复合材料,其特征在于:该复合材料由具有十二面体结构的碳骨架及钴钼双金属磷化物纳米颗粒构成。
2.如权利要求1所述的碳-钴钼双金属磷化物复合材料,其特征在于:所述碳-钴钼双金属磷化物复合材料是Co-Mo-P-C,其中的双金属磷化物纳米颗粒由MoP、CoP、以及CoMoP2纳米颗粒组成。
3.一种权利要求1所述的碳-钴钼双金属磷化物复合材料的制备方法,其特征在于,按照以下步骤制备:
1)按照质量比1∶1-3称取Co(NO3)2·6H2O和2-甲基咪唑,然后分别将其溶于甲醇中,待搅拌溶解后,将2-甲基咪唑溶液倒入Co(NO3)2溶液中搅拌,停止搅拌后在室温下老化24h,之后将产物离心分离并清洗、干燥,得到具有十二面体结构的Co基有机化合物;
2)将MoO3与步骤1)得到的Co-C有机化合物置于石英舟中放入管式电阻炉,之后将其置于氩气氛围中升温至700-900℃,并保温1-4h,从而得到含有MoO2、Mo2C与Co单质的Co-Mo-C复合材料;
3)将上述Mo-Co-C复合材料与磷酸氢二铵分别按照1-3∶5-8的质量比置于磁舟的两端,将磁舟放置于管式炉内,在氢气气氛下升温至720-950℃并保温1-3h进行磷化,待冷却至室温后得到碳复合双金属磷化物材料Co-Mo-P-C。
4.如权利要求3所述的碳-钴钼双金属磷化物复合材料的制备方法,其特征在于:步骤1)中所述清洗干燥为采用甲醇洗涤3次,然后在60℃下真空干燥8h。
5.如权利要求3所述的碳-钴钼双金属磷化物复合材料的制备方法,其特征在于:步骤2)中MoO3的加入量为120mg,Co基有机化合物的加入量40mg,并在氩气氛围中以5℃/min的升温速率,升温至800℃,并保温2h。
6.如权利要求3所述的碳-钴钼双金属磷化物复合材料的制备方法,其特征在于:在步骤2)中中MoO3的加入量为120-150mg,并在氩气氛围中升温至800℃,保温2h。
7.一种如权利要求1或2之一所述的碳-钴钼双金属磷化物复合材料或如权利要求3-6任一所述方法制备得到的碳-钴钼双金属磷化物复合材料的用途,其特征在于:该碳-钴钼双金属磷化物复合材料应用于电催化制氢领域。
8.一种催化剂材料,其特征在于:包括权利要求1或2之一所述的碳-钴钼双金属磷化物复合材料。
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