CN114540863A - 一种钌负载掺氮多孔碳析氢电催化剂的制备方法 - Google Patents
一种钌负载掺氮多孔碳析氢电催化剂的制备方法 Download PDFInfo
- Publication number
- CN114540863A CN114540863A CN202210041737.2A CN202210041737A CN114540863A CN 114540863 A CN114540863 A CN 114540863A CN 202210041737 A CN202210041737 A CN 202210041737A CN 114540863 A CN114540863 A CN 114540863A
- Authority
- CN
- China
- Prior art keywords
- nhpc
- nitrogen
- porous carbon
- preparation
- doped porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229920002472 Starch Polymers 0.000 claims abstract description 9
- 239000008107 starch Substances 0.000 claims abstract description 9
- 235000019698 starch Nutrition 0.000 claims abstract description 9
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000001393 triammonium citrate Substances 0.000 claims abstract description 6
- 235000011046 triammonium citrate Nutrition 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 5
- 229910019891 RuCl3 Inorganic materials 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 3
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 239000012258 stirred mixture Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种钌负载掺氮多孔碳析氢电催化剂的制备方法,取可溶性淀粉、柠檬酸三铵和碳酸氢钠混合并充分搅拌,在氮气气氛下,700℃~900℃高温炭化,产物加入去离子搅拌,过滤并水洗滤渣至pH=6~8,干燥,得到NHPC;NHPC和RuCl3·3H2O溶于去离子水超声分散,将NaBH4溶液缓慢的滴加到超声氛围中的混合液中,洗涤反应物料,干燥后得到最终产物。优点是:工艺简单,制备的催化剂孔径由几纳米到几百纳米不等,且呈现随机无序状态分布,丰富的孔道结构不仅有利于反应中气体和反应物的快速扩散,还有利于电解液对催化剂的浸润,缩短电子和电荷的输运距离,提高反应速率和催化稳定性。
Description
技术领域
本发明属于电催化析氢技术领域,尤其涉及一种Ru/NHPC钌负载掺氮多孔碳析氢电催化剂的制备方法。
背景技术
氢能作为一种新型能源,具有原料丰富、能量密度高、应用范围广等特点。水的电解制氢是实现工业化廉价制备氢气的重要手段,而在电解制备过程中缓慢的HER动力学能垒往往需要高效的催化剂来降低化学反应能耗。常见的析氢催化剂中,Pt/C催化剂有着极高的催化活性,但由于其在地壳中的丰度很低,资源稀缺,价格昂贵,从而限制其大规模使用。因此,寻找价格低廉且催化性能良好的HER催化剂成为近年来研究的热点。
Ru与氢的结合能约为65kcal/mol,且与Pt相近,同时,Ru具有强大的防腐能力,可用于各种常用的电解质中,是一种极具应用前景的HER催化剂。优异的HER催化剂往往具有较低的析氢过电位和塔菲尔斜率,并且具有良好的长期稳定性。虽然贵金属Pt、Ru、Ir等拥有丰富的催化活性位点,但由于其溶解速率较高,可能导致稳定性差,并且在较长时间的催化过程中发生奥斯瓦尔德熟化、团聚以及催化剂脱落等问题而使催化剂的稳定性变差。
发明内容
为克服现有技术的不足,本发明的目的是提供一种钌负载掺氮多孔碳析氢电催化剂的制备方法,制备的Ru/NHPC催化剂避免了传统的高温烧结,并获得了优异的电化学析氢性能和稳定性。
为实现上述目的,本发明通过以下技术方案实现:
一种钌负载掺氮多孔碳析氢电催化剂的制备方法,包括:
1)NHPC的制备
取可溶性淀粉、柠檬酸三铵和碳酸氢钠混合并充分搅拌,将搅拌后的混合物转移至管式炉中,在氮气气氛下,以5~15℃/min的升温速率升温,在700℃~900℃高温炭化1~2h,将炭化后的产物加入去离子水室温下搅拌1~4h,过滤并水洗滤渣至pH=6~8,在70~90℃温度下干燥;
2)Ru/NHPC催化剂材料的制备
取步骤1)制得的NHPC掺氮多孔碳和RuCl3·3H2O溶于去离子水,在超声的氛围下超声分散;配置2mg/ml的NaBH4溶液,将NaBH4溶液缓慢的滴加到超声氛围中的混合液中;滴加完成后,将混合液在超声氛围中持续反应20~60min;最后,分别用去离子水和无水乙醇洗涤反应物各3次,70~90℃下干燥后得到最终产物Ru/NHPC催化剂材料。
所述的可溶性淀粉为1~3g;柠檬酸三铵为2~8g;碳酸氢钠为2~8g。
步骤2)所述的NHPC掺氮多孔碳为0.05~0.2g;RuCl3·3H2O为0.01~0.1g;NaBH4溶液为0.01~0.1g。
与现有技术相比,本发明的有益效果是:
本发明工艺简单,通过发泡法制备掺氮多孔碳材料,再通过超声辅助沉淀法将Ru均匀的分散在掺氮的多孔碳上,制备了高性能的Ru/NHPC催化剂。该催化剂孔径由几纳米到几百纳米不等,且呈现随机无序状态分布。经BET的测试评价发现该掺氮多孔碳材料具有非常大的比表面积(m2/g)。大的比表面积有利于暴露更多的活性位点,提高催化性能;多孔碳丰富的孔道结构不仅有利于反应中气体和反应物的快速扩散,还有利于电解液对催化剂的浸润,缩短电子和电荷的输运距离,提高反应速率和催化稳定性;N原子的引入进一步调节复合材料的电子结构,使Ru基催化剂表现出优异的性能。这些特点使催化剂不仅具有较低的析氢过电位,而且拥有良好的稳定性,并且在碱性环境下表现出优异的电催化析氢性能和稳定性。拓展了电催化制氢技术领域的应用,即符合社会发展的需要,又具有良好的经济效益。
本技术采用廉价的生物质可溶性淀粉为碳源,柠檬酸三铵为发泡剂和氮源,碳酸氢钠为发泡剂制备出具有大比表面积的掺氮多孔碳。在高温加热过程中通过碳酸氢钠分解产生的二氧化碳和柠檬酸三铵分解产生的氨气对和可溶性淀粉进行发泡造孔,同时产生的氨气进一步沉积在炭化材料表面对多孔炭材料进行氮元素的掺杂。制备出的大比表面积掺氮多孔碳,一方面降低了制备成本,另一方面丰富的孔道结构更有利于活性位点均匀的分散。以RuCl3·3H2O为Ru源,NaBH4为还原剂,通过超声辅助沉淀法制备的Ru/NHPC催化剂材料。此方法避免了传统的高温烧结,并获得了优异的电化学析氢性能和稳定性,为其它电催化析氢材料的制备提出了一定的借鉴意义和想法。
附图说明
图1是三电极测试体系组装、流程图。
图2是掺氮多孔碳(NHPC)的XRD图。
图3是钌负载掺氮多孔碳(Ru/NHPC)的XRD图。
图4是掺氮多孔碳(NHPC)的SEM图。
图5是掺氮多孔碳(NHPC)的EDS图。
图6是钌负载掺氮多孔碳(Ru/NHPC)的SEM图。
图7是钌负载掺氮多孔碳(Ru/NHPC)的EDS图。
图8是钌负载掺氮多孔碳(Ru/NHPC)的LSV曲线图。
图9是钌负载掺氮多孔碳(Ru/NHPC)的Tafel曲线图。
图10是钌负载掺氮多孔碳(Ru/NHPC)的稳定性测试图。
具体实施方式
下面结合说明书附图对本发明进行详细地描述,但是应该指出本发明的实施不限于以下的实施方式。
实施例1
取2g可溶性淀粉,6g柠檬酸铵,6g碳酸氢钠倒入烧杯中,搅拌使其均匀的混合在一起。然后将混合物转移至管式炉中,在N2的氛围下,以10℃/min的升温速率将混合物直接加热到800℃,并在800℃下保温1h。将冷却好的材料转移至烧杯中,加入500ml去离子水并在室温下充分搅拌2h。最后,抽滤并用去离子水洗涤滤饼至中性,在80℃烘箱中干燥12h,得到最终的NHPC产物。
取0.05gRuCl3·3H2O和0.1g步骤1制备的NHPC放入烧杯中,加入50ml去离子水,并将混合物超声分散10min。将25ml浓度为2mg/ml的NaBH4溶液缓慢滴入混合液中。滴加完成后,继续超声30min。抽滤并用去离子水和无水乙醇各洗涤3次,在80℃烘箱中干燥12h,将催化剂材料Ru/NHPC命名为Ru/NHPC-0.05。
实施例2
取2g可溶性淀粉,3g柠檬酸铵,3g碳酸氢钠倒入烧杯中,搅拌使其均匀的混合在一起。然后将混合物转移至管式炉中,在N2的氛围下,以10℃/min的升温速率将混合物直接加热到800℃,并在800℃下保温1h。将冷却好的材料转移至烧杯中,加入500ml去离子水并在室温下充分搅拌2h。最后,抽滤并用去离子水洗涤滤饼至中性,在80℃烘箱中干燥12h,得到最终的NHPC产物。
其他的步骤同实施例1。
实施例3
掺氮多孔碳(NHPC)同实施例1。
取0.02gRuCl3·3H2O和0.1g制备的掺氮多孔碳NHPC放入烧杯中,加入50ml去离子水,并将混合物超声分散10min。将10ml浓度为2mg/ml的NaBH4溶液缓慢滴入混合液中。滴加完成后,继续超声30min。抽滤并用去离子水和无水乙醇各洗涤3次,在80℃烘箱中干燥12h,将催化剂材料Ru/NHPC命名为Ru/NHPC-0.02。
图1,析氢电催化剂的三电极体系,包括工作电极的制备电解池装置组装的过程,具体如下:
(1)催化剂悬浮液的制备:称5mg实施例1-3制备的任意一种催化剂材料,分散在700μL异丙醇、200μL去离子水和100μLNafion溶液(5%)的混合溶液中超声处理1h。
(2)工作电极的制备:分别采用粒径为1μm、0.5μm和50nm的Al2O3抛光粉打磨直径为5mm的L型玻碳电极,每次打磨后先洗去表面污物,再使用乙醇水溶液(v:v=1:1)在超声水浴下清洗电极表面并使用氮气吹干电极表面。移取10μL催化剂悬浮液滴在玻碳电极表面,待室温下自然干燥。
(3)电解液的配置:配置1M KOH溶液,在氮气下鼓泡30min。
将涂有催化剂悬浮液的玻碳电极(工作电极)、Ag/AgCl电极(参比电极)和铂电极(对电极)插入氮气吹扫后的1M KOH溶液中。采用在析氢电位范围内扫描CV曲线进行电极活化。
见图2,从图中可以看出两个明显的衍射峰,分别对应石墨C的(002)和(101)晶面。
见图3,与图2相比,新出现的特征峰与Ru-PDF#01-089-3942的特征峰相对应,说明Ru成功负载到掺氮多孔碳。
见图4,从图中可以看出,NHPC为三维分布的多孔碳骨架,整体碳骨架孔径由几纳米到几百纳米不等,呈现随机无序状态分布。由BET吸附等温方程可以测得NHPC的比表面积为1456.03m2 g-1。
见图5,从图中可以看出,C、N元素均匀的分布在材料表面。
见图6,与图4对比可以看出复合后材料仍旧呈现三维无序分布的多空结构,由BET吸附等温方程可以测得Ru/NHPC的比表面积为1303.103m2 g-1,说明Ru的负载没有对Ru/NHPC催化剂的孔道结构造成明显影响。
见图7,从图中可以看出,C、N、Ru元素均匀的分布在材料表面。进一步说明单质Ru成功负载到NHPC。
见图8,从图中可以看出,在10mA cm-2的电流密度下,复合材料的过电位为33mV。
见图9,从图中数据计算可得复合材料的Tafel斜率b为36mV dec-1。
见图10,从图中可以看出,复合材料在进行了1000次的CV循环后,LSV曲线几乎不发生衰减,说明Ru/NHPC复合材料具有良好的稳定性。
Claims (3)
1.一种钌负载掺氮多孔碳析氢电催化剂的制备方法,其特征在于,包括:
1)NHPC的制备
取可溶性淀粉、柠檬酸三铵和碳酸氢钠混合并充分搅拌,将搅拌后的混合物转移至管式炉中,在氮气气氛下,以5~15℃/min的升温速率升温,在700℃~900℃高温炭化1~2h,将炭化后的产物加入去离子水室温下搅拌1~4h,过滤并水洗滤渣至pH=6~8,在70~90℃温度下干燥;
2)Ru/NHPC催化剂材料的制备
取步骤1)制得的NHPC掺氮多孔碳和RuCl3·3H2O溶于去离子水,在超声的氛围下超声分散;配置2mg/ml的NaBH4溶液,将NaBH4溶液缓慢的滴加到超声氛围中的混合液中;滴加完成后,将混合液在超声氛围中持续反应20~60min;最后,分别用去离子水和无水乙醇洗涤反应物各3次,70~90℃下干燥后得到最终产物Ru/NHPC催化剂材料。
2.根据权利要求1所述的一种钌负载掺氮多孔碳析氢电催化剂的制备方法,其特征在于,所述的可溶性淀粉为1~3g;柠檬酸三铵为2~8g;碳酸氢钠为2~8g。
3.根据权利要求1所述的一种钌负载掺氮多孔碳析氢电催化剂的制备方法,其特征在于,步骤2)所述的NHPC掺氮多孔碳为0.05~0.2g;RuCl3·3H2O为0.01~0.1g;NaBH4溶液为0.01~0.1g。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210041737.2A CN114540863B (zh) | 2022-01-14 | 2022-01-14 | 一种钌负载掺氮多孔碳析氢电催化剂的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210041737.2A CN114540863B (zh) | 2022-01-14 | 2022-01-14 | 一种钌负载掺氮多孔碳析氢电催化剂的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114540863A true CN114540863A (zh) | 2022-05-27 |
CN114540863B CN114540863B (zh) | 2024-03-08 |
Family
ID=81672436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210041737.2A Active CN114540863B (zh) | 2022-01-14 | 2022-01-14 | 一种钌负载掺氮多孔碳析氢电催化剂的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114540863B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116273052A (zh) * | 2023-03-21 | 2023-06-23 | 福州大学 | 一种过渡金属负载的钙钛矿型催化剂的制备及其应用 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104689857A (zh) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | 氮掺杂多孔碳材料的制备方法以及含该材料的催化剂及用途 |
CN106179440A (zh) * | 2016-06-24 | 2016-12-07 | 浙江大学 | 氮掺杂多级孔炭及其制备方法和应用 |
CN109453811A (zh) * | 2018-10-31 | 2019-03-12 | 郑州大学第附属医院 | 一种双功能复合电解水催化剂、制备方法及其应用 |
CN110055556A (zh) * | 2018-04-28 | 2019-07-26 | 南方科技大学 | 析氢反应催化剂及其制备方法和应用 |
CN110813359A (zh) * | 2019-11-22 | 2020-02-21 | 福州大学 | 一种以氮掺杂多孔碳材料为载体的钌基氨合成催化剂及其制备方法 |
CN110813350A (zh) * | 2019-10-25 | 2020-02-21 | 江苏大学 | 一种碳基复合电催化剂及其制备方法与应用 |
WO2020042526A1 (zh) * | 2018-08-31 | 2020-03-05 | 浙江新和成股份有限公司 | 复合催化剂及其制备方法、应用 |
WO2020072291A1 (en) * | 2018-10-02 | 2020-04-09 | The Regents Of The University Of California | Ruthenium and nitrogen doped carbon matrix catalyst and methods for making and using thereof |
CN113684502A (zh) * | 2021-09-19 | 2021-11-23 | 华东理工大学 | 一种用于电解析氢的氮掺杂碳基负载钌催化剂的制备方法 |
CN113862693A (zh) * | 2021-10-13 | 2021-12-31 | 中国海洋大学 | 一种氮掺杂介孔碳负载高分散Ru纳米颗粒催化剂的制备方法及其应用 |
-
2022
- 2022-01-14 CN CN202210041737.2A patent/CN114540863B/zh active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104689857A (zh) * | 2015-03-26 | 2015-06-10 | 中国科学院青岛生物能源与过程研究所 | 氮掺杂多孔碳材料的制备方法以及含该材料的催化剂及用途 |
CN106179440A (zh) * | 2016-06-24 | 2016-12-07 | 浙江大学 | 氮掺杂多级孔炭及其制备方法和应用 |
CN110055556A (zh) * | 2018-04-28 | 2019-07-26 | 南方科技大学 | 析氢反应催化剂及其制备方法和应用 |
WO2020042526A1 (zh) * | 2018-08-31 | 2020-03-05 | 浙江新和成股份有限公司 | 复合催化剂及其制备方法、应用 |
WO2020072291A1 (en) * | 2018-10-02 | 2020-04-09 | The Regents Of The University Of California | Ruthenium and nitrogen doped carbon matrix catalyst and methods for making and using thereof |
CN109453811A (zh) * | 2018-10-31 | 2019-03-12 | 郑州大学第附属医院 | 一种双功能复合电解水催化剂、制备方法及其应用 |
CN110813350A (zh) * | 2019-10-25 | 2020-02-21 | 江苏大学 | 一种碳基复合电催化剂及其制备方法与应用 |
CN110813359A (zh) * | 2019-11-22 | 2020-02-21 | 福州大学 | 一种以氮掺杂多孔碳材料为载体的钌基氨合成催化剂及其制备方法 |
CN113684502A (zh) * | 2021-09-19 | 2021-11-23 | 华东理工大学 | 一种用于电解析氢的氮掺杂碳基负载钌催化剂的制备方法 |
CN113862693A (zh) * | 2021-10-13 | 2021-12-31 | 中国海洋大学 | 一种氮掺杂介孔碳负载高分散Ru纳米颗粒催化剂的制备方法及其应用 |
Non-Patent Citations (2)
Title |
---|
ZIQI ZHANG 等: "One-pot synthesis of ruthenium nanoparticles embedded nitrogen-doped carbon framework for electrocatalytic hydrogen evolution reaction", INORGANIC CHEMISTRY COMMUNICATIONS, pages 1 - 7 * |
姚俊杰 等: "电解水制氢中钌基电催化剂的研究进展", 电池工业, vol. 23, no. 3, pages 151 - 156 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116273052A (zh) * | 2023-03-21 | 2023-06-23 | 福州大学 | 一种过渡金属负载的钙钛矿型催化剂的制备及其应用 |
Also Published As
Publication number | Publication date |
---|---|
CN114540863B (zh) | 2024-03-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108486605A (zh) | 一种具有优异电解水性能的碳包覆硒化镍钴纳米材料及其制备方法 | |
CN110993968B (zh) | 一种碳气凝胶单金属原子催化剂的制备方法及电催化应用 | |
CN110075853B (zh) | 一种电催化全分解水CoZn-LDHs-ZIF@C复合结构材料及制备方法、应用 | |
CN104923204A (zh) | 一种石墨烯包覆金属纳米粒子催化剂的制备方法及其应用 | |
CN108048866A (zh) | 氮掺杂多孔碳包覆的钴铱核壳结构纳米颗粒的制备及其催化水裂解应用 | |
CN111744519A (zh) | 一种三维MXene基载体的析氢催化剂的制备方法 | |
CN112993283B (zh) | 过渡金属氮掺杂碳基催化剂及其制备方法和应用 | |
CN102024955B (zh) | 一种用于燃料电池的三维网状纳米多孔钯钌电极材料及其制备方法 | |
CN114108004B (zh) | 一种钌基合金催化剂及其制备方法和应用 | |
CN114522706A (zh) | 一种碳化物负载贵金属单原子催化剂及制备和应用 | |
CN114293223A (zh) | 一种由簇基框架材料制备超细二氧化铈担载金属单原子催化剂的方法 | |
CN111215104A (zh) | 一种磷掺杂碳负载钼钨碳化物催化剂及制备和应用 | |
CN113881965A (zh) | 一种以生物质碳源为模板负载金属纳米颗粒催化剂及其制备方法和应用 | |
Zou et al. | Maximizing Fe-N exposure by tuning surface composition via twice acid treatment based on an ultrathin hollow nanocarbon structure for highly efficient oxygen reduction reaction | |
CN114892202B (zh) | 一种MOFs衍生多孔碳电催化剂及其制备方法和应用 | |
CN114517304B (zh) | 具有PdCu合金颗粒负载的NiFe-LDH金属纳米片材料电催化剂制备方法 | |
Ma et al. | Ni single‐atom arrays as self‐supported electrocatalysts for CO2RR | |
He et al. | Fabrication of hierarchically flower-like trimetallic coordination polymers via ion-exchange strategy for efficient electrocatalytic oxygen evolution | |
CN114540863B (zh) | 一种钌负载掺氮多孔碳析氢电催化剂的制备方法 | |
CN114164452A (zh) | 一种制备超薄钒酸钴纳米片负载金属单原子催化剂的方法 | |
CN113136598A (zh) | 一种碳负载镍锌氮化物双功能催化剂及其制备方法和应用 | |
CN110038612B (zh) | 一种n掺杂微孔碳球orr催化材料及其制备方法和应用 | |
CN109201054B (zh) | 一种自支撑型双金属催化剂及其制备方法和应用 | |
CN108842165B (zh) | 溶剂热法制备硫掺杂的NiFe(CN)5NO电解水析氧催化剂及其应用 | |
CN114068950B (zh) | 基于多孔碳支撑的超细亚纳米金复合材料电催化剂及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |