CN115404491A - 一种片状多组分复合材料的制备与应用 - Google Patents
一种片状多组分复合材料的制备与应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000004332 silver Substances 0.000 claims abstract description 27
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
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- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910001923 silver oxide Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 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 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
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- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 7
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- 238000011161 development Methods 0.000 abstract description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 150000003346 selenoethers Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
本发明提供了一种片状多组分复合材料的制备方法,是将硝酸银、钴盐和尿素完全溶解于水中后,在140‑180℃下进行水热处理制得前驱体,再对前驱体进行氧化,钴的氢氧化物分解生成片状钴的氧化物,得银/钴复合氧化物。最后进行磷化,含磷盐分解产生还原性含磷气体对银/钴复合氧化物进行还原和磷化,最终得到Ag/CoO/CoP/Co2P复合材料。本发明所得复合催化剂贵金属Ag含量低,含有多种活性组分,活性位点丰富,片状结构有利于暴露更多活性位点。所得复合催化剂在碱性介质中对电解水析氢、析氧及水的全分解均具有优异的电催化活性和良好的稳定性,在电解水制氢技术中具有很好的发展前景。
Description
技术领域
本发明涉及片状多组分复合材料的制备与应用,尤其涉及制备一种微量银修饰的Ag/CoO/CoP/Co2P四组分片状复合材料,主要用作碱性介质中电解水析氢反应(HER)、析氧反应(OER)及水的全分解反应。
背景技术
氢能因其来源广泛、能量密度高、无污染、可持续性强,被认为是一种替代化石能源,缓解全球能源危机及气候变化等环境问题的清洁能源。电解水作为最具前景的清洁制氢技术,受到了全世界的广泛重视和研究。电解水由两个半反应组成,即析氢反应(HER)和析氧反应(OER)。由于HER和OER的反应速率低、过电位高,限制了电解水的整体效率和大规模应用。因此,发展性能优良的HER和OER电催化剂是电解水制氢发展的核心技术。目前,贵金属催化剂Pt/C和RuO2/IrO2分别被认为是最高效的HER和OER催化剂。但由于其储量稀少、成本高、稳定性差,不能满足大规模使用的需求。因此,开发活性高、稳定性好、价格低、制备方法简单的HER和OER双功能催化剂,是推动电解水制氢技术大规模商业化的迫切需求。
过渡金属化合物因其结构多样、储量丰富和电催化性能可调而被广泛研究。过渡金属硼化物、碳化物、氮化物、氧化物、硫化物、磷化物、硒化物及其合金等均被证明可以作为HER或OER的电催化剂。然而,单一组分催化剂的组成、结构及催化活性可调性有限,加之过渡金属化合物普遍存在导电性差的缺点,很难达到商业化的要求。另外,形貌和结构对催化剂的活性提高也至关重要。普遍认为,纳米片状结构和介孔结构有利于暴露更多的活性位点,促进传质和电荷的转移,从而提高催化剂的活性。过渡金属磷化物结构丰富、对HER和OER具有较高的催化活性。尤其是CoP和Co2P具有良好的催化活性,但其导电性差、易因被氧化而失活。而在诸多金属中,银具有非常高的导电性,且其成本低于其它贵金属,在碱性条件下具有优异的电化学稳定性。CoO也具有良好的OER催化活性和优良的抗氧化性。基于以上分析,发展一种简便可行的方法将Ag、CoO、CoP和Co2P进行有效的复合,制备Ag/CoO/CoP/Co2P复合催化剂,通过调节各组分的含量来制备高效、稳定的HER和OER双功能电催化剂具有非常重要的意义。
发明内容
本发明的目的是提供一种简便可控地制备片状微量银修饰的过渡金属磷化物/氧化物复合材料Ag/CoO/CoP/Co2P双功能催化剂的方法以及测试所制备复合催化剂催化HER、OER及电解水的性能。
一、片状多组分复合材料的制备
本发明片状多组分复合材料的制备,包括以下工艺步骤:
(1)前驱体的制备:将硝酸银、钴盐和尿素完全溶解于水中形成溶液,然后将溶液转移至带有聚四氟乙烯内衬的反应釜中,在140-180 ℃下水热处理10-14h。在此过程中,尿素提供了碱性环境和导向作用,使钴盐水解生成片状氢氧化物,微量的Ag+转化成Ag2O沉积在钴的氢氧化物上。反应结束后,将固体产物用蒸馏水和乙醇充分洗涤后在100℃下真空干燥即可制得前驱体。
其中尿素既是沉淀剂,又是导向剂;钴盐为CoCl2·6H2O、Co(CH3COO)2·4H2O、Co(acac)3、Co(NO3)2·6H2O中的一种;尿素的物质的量为硝酸银和钴盐物质的量之和的1-3倍;钴盐的物质的量为硝酸银物质的量的10-20倍。
(2)前驱体的氧化:将上述所制备的前驱体置于马弗炉中在400-500℃(优选420℃)下氧化2-5 h(优选3 h),升温速率为2-5℃/min(优选3 ℃/min)。在此过程中,钴的氢氧化物分解生成钴的氧化物,得银/钴氧化物。
(3)片状多组分复合材料的制备:将所制备的银/钴氧化物置于管式炉中,在N2中,250-400℃(优选350℃)下磷化2-5 h(优选3 h),升温速率为2-5℃/min(优选3 ℃/min),以含磷盐为磷源进行磷化得到最终的复合材料。
含磷盐为次亚磷酸钠、磷酸氢二钠、磷酸二氢钾、磷酸钠中的一种。含磷盐的质量为银/钴氧化物质量的10~20倍。
所制备复合材料由厚度在100-200 nm的薄片直立、错综堆积而成,由单质Ag、CoO、CoP和Co2P四种组分组成。其中,Ag的含量为1-1.5%,CoO的含量为13-25%,CoP的含量为32-46%,Co2P的含量为45-52%;复合材料纳米片由粒径在40-50 nm的各组分的纳米粒子堆积而成,堆积孔的孔径主要集中在5-12 nm的介孔范围内;复合材料的比表面积为20-25m2/g,孔容为0.03-0.05cm3/g。
二、片状多组分复合材料的结构
图1是本发明实施例1所制备催化剂的SEM图。由图可知,所制备催化剂为由厚度在100-200 nm的薄片直立、错综堆积而成。
图2是本发明实施例1所制备催化剂的TEM图。由图可知,复合材料纳米片由粒径在40-50 nm的各组分的纳米粒子堆积而成。
图3是本发明实施例1-4所制备催化剂的XRD图:(a) 实施例1;(b) 实施例2;(c)实施例3和(d) 实施例4。由图可知,所制备的三种催化剂均由Ag、CoO、CoP和Co2P四种组分组成。在2θ约为38.1°, 44.3°, 64.4°, 77.4° 和 81.5° 处的峰分别归属于Ag的(111),(200), (220), (311) 和 (222) 晶面衍射峰 (JCPDS No. 04-0783);在2θ 约为36.5°,42.4°, 61.5°, 73.7° 和 77.6° 处的衍射峰分别归属于CoO的 (111), (200), (220),(311) 和 (222) 晶面的衍射峰 (JCPDS No. 65-2902);在2θ约为31.6°, 36.3°, 46.2°,48.1°, 52.3°, 56.0°, 59.9° 和 61.7° 处的峰分别归属于CoP (011), (111), (112),(211), (103), (020), (113) 和 (203) 晶面的衍射峰 (JCPDS No.65-1474);在2θ 约为40.8° 和 48.4° 处的峰分别归属于Co2P的(111)和(120) 晶面的衍射峰(JCPDS No. 54-0413).
图4是本发明实施例1所制备催化剂的N2吸脱附等温线和孔径分布图。由图可知,所得样品表现出II型等温线和H3回滞环,说明样品具有丰富的孔道结构。孔径分布曲线进一步显示,该样品的孔径主要集中在5-12 nm的介孔范围内。该样品的比表面积为22.7 m²/g,孔容为0.035cm3/g。
三、片状多组分复合材料的电催化性能测试
1、电解水析氢性能测试
将所得复合材料制作成电催化析氢、析氧及电解水工作电极:将一定量的复合材料超声分散到乙醇中,加入适量的5% Nafion溶液混合均匀制成悬浊液。将一定量该悬浊液滴涂在玻碳电极上,自然晾干制成用于电催化析氢、析氧的工作电极,用三电极体系进行测试;将一定量该悬浊液滴涂在处理好的泡沫镍上制成用于电催化分解水的工作电极,用两电极体系进行测试。所有电化学测试均使用CHI760E电化学工作站完成。
图5是本发明实施例1所制备催化剂在1 M KOH中催化HER的LSV曲线。由图可知该催化剂在1 M KOH中催化HER时,电流密度达到10 mA /cm2时的过电位是107mV。证明该催化剂对HER具有优异的催化活性。
图6是本发明实施例1所制备催化剂在1 M KOH中催化OER的LSV曲线。由图可知该催化剂在1 M KOH中催化OER时,电流密度达到10 mA /cm2时的过电位是166 mV。证明该催化剂对OER具有优异的催化活性。
图7是本发明实施例1所制备催化剂在1 M KOH中催化电解水的LSV曲线。由图可知,所得催化剂在1 M KOH中催化水的全分解时,电流密度达到10 mA/cm2时的分解电压为1.47 V,证明该催化剂作为HER和OER双功能催化剂,对电解水具有优异的催化活性。
图8是本发明实施例1所制备催化剂在1 M KOH中催化电解水的相对电流密度-时间曲线。由图可知,所得催化剂在经过10h稳定性测试后,其电流密度只降低了7.2%,证明该催化剂在催化电解水的过程中具有良好的稳定性。
以上测试结果表明,在1 M KOH溶液中,在10 mA/cm2的电流密度下,所制备催化剂催化HER的过电位可低至107mV,催化OER的过电位可低至166mV,电解水的分解电压可低至1.43 V,并且具有良好的循环稳定性。
本发明的反应机理为:将硝酸银、钴盐和尿素完全溶解于水中后,在140-180 ℃下水热处理的过程中,尿素提供了碱性环境和导向作用,使钴盐水解生成片状氢氧化物,微量的Ag+转化成Ag2O沉积在钴的氢氧化物上制得前驱体。在前驱体被氧化的过程中,钴的氢氧化物分解生成片状钴的氧化物,得银/钴复合氧化物。在对银/钴复合氧化物进行磷化的过程中,含磷盐分解产生还原性含磷气体对银/钴复合氧化物进行还原和磷化,最终得到Ag/CoO/CoP/Co2P复合材料。通过控制金属盐的比例及含磷盐与银/钴氧化物的质量比,可以调控各组分的比例和复合材料的组成。
本发明与现有技术相比具有以下优点:
1、用简单的方法原位制备了片状Ag/CoO/CoP/Co2P四组分复合材料。和分步复合及后修饰的方法相比,原位制备的方法可使各组分间形成异质界面结构,有利于调节各活性位点的电子结构,促进电荷的转移和传输,从而提高催化剂的本征活性及反应动力学速率,赋予了催化剂优异的催化HER、OER和水的全分解的活性和稳定性。
2、OER反应被认为是电解水的决速反应,复合材料中CoP、Co2P和CoO均可高效催化OER反应,CoP和Co2P同时也是高效的HER催化剂。因此,复合材料中各组分间的协同作用使其获得了更高的催化活性。
3、Ag的加入可以极大提高催化剂的导电性,从而提高电荷传输速率,加快反应速率。
4、片状多孔结构有利于活性位点的暴露,减小传质和电荷传输的阻力,进而提高其催化活性。
5、Ag的含量低至1-1.5%,且Ag是相对廉价的贵金属,使得本发明所制备的复合材料具有很高的性价比。
6、活性测试表明,本发明制备的复合材料对HER、OER和水的全分解反应都具有很高的电催化活性,在碱性介质中均具有良好的稳定性,因此是一种发展前景良好的电解水催化剂。
附图说明
图1是本发明实施例1所制备催化剂的SEM图。
图2是本发明实施例1所制备催化剂的TEM图。
图3是本发明实施例1-4所制备催化剂的XRD图谱。
图4是本发明实施例1所制备催化剂的N2吸脱附等温线和孔径分布图。
图5是本发明实施例1所制备催化剂在1 M KOH中催化HER的LSV曲线。
图6是本发明实施例1所制备催化剂在1 M KOH中催化OER的LSV曲线。
图7是本发明实施例1所制备催化剂在1 M KOH中催化电解水的LSV曲线。
图8是本发明实施例1所制备催化剂在1 M KOH中催化电解水的相对电流密度-时间曲线。
具体实施方式
下面通过具体实施例对本发明片状多组分复合材料的制备与应用作更详细的描述。
实施例1
(1)前驱体的制备:称取AgNO3(0.041 g, 0.24mmol),Co(NO3)2·6H2O (1.051 g,3.61mmol)和CH4N2O (0.463 g, 7.7 mmol)完全溶解于60 mL的去离子水中形成溶液。Co(NO3)2·6H2O的物质的量是AgNO3的15.0倍,尿素的物质的量是硝酸盐物质的量总和的2倍。将溶液转移至80 mL反应釜中,在160℃下保持12 h。反应结束后,离心分离,将固体产物用蒸馏水和乙醇洗涤后,在100 ℃下真空干燥即可制得前驱体。
(2)前驱体的氧化:将上述所制备的前驱体置于马弗炉中,空气气氛下以3℃/min的速率升温至420 ℃保持氧化3 h,即可得到银/钴氧化物。
(3)片状多组分复合材料的制备:取0.1 g所制备的银/钴氧化物置于管式炉中部,另取1.5 g次亚磷酸钠置于管式炉进气口一端,次亚磷酸钠的质量为银/钴氧化物质量的15倍。在N2中,以3 ℃/min 的速率升温至350℃保持3h,得到最终的片状复合材料。所得复合材料的SEM图如图1所示,TEM图如图2所示,其组成为Ag (1.3%),CoO(17.4%)、CoP(42.2%)和Co2P(39.1%)(图3),比表面积为22.8 m2/g,孔体积为0.040 cm3/g(图4)。
(4)催化性能测试
测试方法:称取5 mg所制备催化剂加入0.5 mL无水乙醇和10 μLNafion(Dupont,5wt%)的溶液中,超声处理30 min,取5 μL悬浊液涂到3 mm玻碳电极上。以涂有催化剂的玻碳电极为工作电极,石墨电极为对电极,Ag/AgCl电极为参比电极,1 M KOH为电解液,采用三电极体系进行HER 和OER测试。测试电解水性能采用两电极体系,取80 μL制好的悬浊液,分别滴涂在两片泡沫Ni(1×1 cm)上,制成阴极和阳极,并在室温下真空干燥后在1 M KOH溶液中进行测试。稳定性测试采用在电流密度为10 mA/cm2时所对应的电位下,测试电流-时间曲线的方法。稳定性以电流密度的降低百分数(即相对电流密度)与时间的关系来表示。
测试结果:在电流密度为10 mA/cm2时,催化HER的过电位为107 mV(图5),催化OER的过电位为166 mV(图6),催化电解水的分解电压为1.43 V(10 mA/cm2时)(图7)。催化剂在经过10h的稳定性测试后,其电流密度只降低了7.2%(图8)。这些结果表明,该催化剂具有优异的催化HER、OER和电解水的活性及稳定性。
实施例2
(1)前驱体的制备:称取AgNO3(0.041 g, 0.24 mmol), Co(NO3)2·6H2O (1.401g, 4.81 mmol), CH4N2O (0.607 g, 10.1mmol) 完全溶解于60 mL的去离子水中形成溶液。Co(NO3)2·6H2O的物质的量是AgNO3的20.0倍,尿素的物质的量是硝酸盐物质的量总和的2倍。将溶液转移至80 mL反应釜中,在160℃下保持12 h。反应结束后,离心分离,将固体产物用蒸馏水和乙醇洗涤后,在100 ℃下真空干燥即可制得前驱体。
(2)前驱体的氧化:将上述所制备的前驱体置于马弗炉中,空气气氛下以3℃/min的速率升温至420 ℃保持氧化3 h,即可得到银/钴氧化物。
(3)片状多组分复合材料的制备:取0.1 g所制备的银/钴氧化物置于管式炉中部,另取1.5 g次亚磷酸钠置于管式炉进气口一端,次亚磷酸钠的质量为银/钴氧化物质量的15倍。在N2中,以3 ℃/min 的速率升温至350 ℃保持3h,得到最终的片状复合材料。所得复合材料的XRD图如图3b所示,其组成为Ag (1.0%),CoO(19.1%)、CoP(39.0%)和Co2P(40.9%),比表面积为24.2 m2/g,孔体积为0.042 cm3/g。
(4)催化性能测试
测试方法:同实施例1。
测试结果:在电流密度为10 mA/cm2时,催化HER的过电位为132 mV,催化OER的过电位为195 mV,催化电解水的分解电压为1.47 V(10 mA/cm2时)。催化剂在经过10h的稳定性测试后,其电流密度降低了11.4%。
实施例3
(1)前驱体的制备:称取AgNO3(0.041 g, 0.24 mmol), Co(NO3)2·6H2O (1.051g, 3.61 mmol), CH4N2O (0.231 g, 3.85mmol) 完全溶解于60 mL的去离子水中形成溶液。Co(NO3)2·6H2O的物质的量是AgNO3的15.0倍,尿素的物质的量是硝酸盐总和的1.0倍。将溶液转移至80 mL反应釜中,在160℃下保持12 h。反应结束后,离心分离,将固体产物用蒸馏水和乙醇洗涤后,在100 ℃下真空干燥即可制得前驱体。
(2)前驱体的氧化:将上述所制备的前驱体置于马弗炉中,空气气氛下以3℃/min的速率升温至420 ℃保持氧化3 h,即可得到银/钴氧化物。
(3)片状多组分复合材料的制备:取0.1 g所制备的银/钴氧化物置于管式炉中部,另取1.5 g次亚磷酸钠置于管式炉进气口一端,次亚磷酸钠的质量为银/钴氧化物质量的15倍。在N2中,以3 ℃/min 的速率升温至350 ℃保持3h,得到最终的片状复合材料。所得复合材料的XRD图如图3c所示,其组成为Ag (1.2%),CoO(16.4%)、CoP(45.3%)和Co2P(37.1%),比表面积为20.8 m2/g,孔体积为0.035 cm3/g。
(4)催化性能测试
测试方法:同实施例1。
测试结果:在电流密度为10 mA/cm2时,催化HER的过电位为162 mV,催化OER的过电位为240 mV,催化电解水的分解电压为1.52V(10 mA/cm2时)。催化剂在经过10h的稳定性测试后,其电流密度降低了16.7%。
实施例4
(1)前驱体的制备:称取AgNO3(0.041 g, 0.24 mmol),Co(NO3)2·6H2O (1.051 g,3.61 mmol), CH4N2O (0.463 g, 7.7 mmol)完全溶解于60 mL的去离子水中形成溶液。Co(NO3)2·6H2O的物质的量是AgNO3的15.0倍,尿素的物质的量是硝酸盐总和的2倍。将溶液转移至80 mL反应釜中,在160℃下保持12 h。反应结束后,离心分离,将固体产物用蒸馏水和乙醇洗涤后,在100 °C下真空干燥即可制得前驱体。
(2)前驱体的氧化:将上述所制备的前驱体置于马弗炉中,空气气氛下以3℃/min的速率升温至420 ℃保持氧化3 h,即可得到银/钴氧化物。
(3)片状多组分复合材料的制备:取0.1 g所制备的银/钴氧化物置于管式炉中部,另取1.0 g次亚磷酸钠置于管式炉进气口一端,次亚磷酸钠的质量为银/钴氧化物质量的10倍。在N2中,以3 ℃/min 的速率升温至350 ℃保持3h,得到最终的片状复合材料。所得复合材料的XRD图如图3d所示,其组成为Ag (1.4%),CoO(24.3%)、CoP(38.4%)和Co2P(35.9%),比表面积为21.5 m2/g,孔体积为0.038 cm3/g。
(4)催化性能测试
测试方法:同实施例1。
测试结果:在电流密度为10 mA/cm2时,催化HER的过电位为193 mV,催化OER的过电位为267 mV,催化电解水的分解电压为1.57V(10 mA/cm2时)。催化剂在经过10h的稳定性测试后,其电流密度降低了8.7%。
Claims (9)
1.一种片状多组分复合材料的制备方法,包括以下工艺步骤:
(1)前驱体的制备:将硝酸银、钴盐和尿素完全溶解于水中形成溶液,然后将溶液在140-180℃下水热处理10-14h后离心分离,将固体产物用蒸馏水和乙醇充分洗涤后,真空干燥即可制得前驱体;
(2)前驱体的氧化:将上述所制备的前驱体置于马弗炉中在400-500℃下氧化2-5 h,升温速率为2-5℃/min,在此过程中即可得到银/钴氧化物;
(3)片状多组分复合材料的制备:将所制备的银/钴氧化物置于管式炉中,在N2气氛中,250-400℃下,升温速率为2-5℃/min,以含磷盐为磷源磷化2-5h,得到最终的复合材料。
2.如权利要求1所述的片状多组分复合材料的制备方法,其特征在于:步骤(1)中,钴盐为CoCl2·6H2O、Co(CH3COO)2·4H2O、Co(acac)3、Co(NO3)2·6H2O中的一种。
3.如权利要求1所述的片状多组分复合材料的制备方法,其特征在于:步骤(1)中,
尿素的物质的量为硝酸银和钴盐物质的量之和的1-3倍;钴盐的物质的量为硝酸银物质的量的10-20倍。
4.如权利要求1所述的片状多组分复合材料的制备方法,其特征在于:步骤(3)中,含磷盐为次亚磷酸钠、磷酸氢二钠、磷酸二氢钾、磷酸钠中的一种。
5.如权利要求1所述的片状多组分复合材料的制备方法,其特征在于:步骤(3)中,含磷盐的质量为银/钴氧化物质量的10~20倍。
6.如权利要求1所述的片状多组分复合材料的制备方法,其特征在于:所制备复合材料由厚度在100-200 nm的薄片直立、错综堆积而成,由单质Ag、CoO、CoP和Co2P四种组分组成;其中,Ag的含量为1-1.5%,CoO的含量为13-25%,CoP的含量为32-46%,Co2P的含量为45-52%。
7.如权利要求1所述方法制备的片状多组分复合材料在电解水析氧反应中的应用。
8.如权利要求1所述方法制备的片状多组分复合材料在电解水析氢反应中的应用。
9.如权利要求1所述方法制备的片状多组分复合材料在电解水全分解反应中的应用。
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