CN112169790B - 原位光还原法制备高负载量的贵金属单原子催化剂的方法 - Google Patents
原位光还原法制备高负载量的贵金属单原子催化剂的方法 Download PDFInfo
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- CN112169790B CN112169790B CN202011082482.1A CN202011082482A CN112169790B CN 112169790 B CN112169790 B CN 112169790B CN 202011082482 A CN202011082482 A CN 202011082482A CN 112169790 B CN112169790 B CN 112169790B
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- 238000000034 method Methods 0.000 title claims abstract description 66
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- 238000007540 photo-reduction reaction Methods 0.000 title claims abstract description 53
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 10
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
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- 150000002367 halogens Chemical class 0.000 claims description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 6
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
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- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
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- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 58
- 229910052697 platinum Inorganic materials 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 15
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- 239000010931 gold Substances 0.000 description 15
- 229910052707 ruthenium Inorganic materials 0.000 description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
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- 238000000354 decomposition reaction Methods 0.000 description 12
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- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000012937 correction Methods 0.000 description 11
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 11
- 239000003504 photosensitizing agent Substances 0.000 description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052741 iridium Inorganic materials 0.000 description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- 210000000078 claw Anatomy 0.000 description 2
- -1 dimethyl (acetylacetone) gold (III) Chemical compound 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- Electromagnetism (AREA)
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Abstract
本发明公开了一种原位光还原法制备高负载量的贵金属单原子催化剂的方法,将氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯经金属盐溶液或金属碱溶液处理使其表面负载钠、钾离子,用去离子水和无水乙醇洗涤至弱碱性后超声分散;再加入贵金属盐溶液以及羰基化合物混合后磁力搅拌;最后在光照条件下进行原位光还原后冷冻干燥,制备贵金属单原子。每0.02~3.0g氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体,加入40~60 ml的摩尔浓度为1~15mol/L的钠或钾的盐溶液或碱溶液。羰基化合物为丙酮、乙酰丙酮、苯乙酮中的任一种。贵金属盐溶液为对应贵金属元素的氯化物或乙酰丙酮盐。获得了高负载量的贵金属单原子。
Description
技术领域
本发明属于光催化剂制备技术领域,涉及一种原位光还原法制备高负载量的贵金属单原子催化剂的方法。
背景技术
在催化领域,单原子催化剂显示出优于传统催化剂的性能。与传统的异质金属/半导体光催化材料不同,单原子光催化剂能够实现金属原子的最大利用率,极大增加光催化剂的活性位点;同时,负载在半导体表面的金属单原子具有独特的不饱和配位环境,呈现出优异的催化活性,提升了每个催化位点的本征活性。自2011年单原子催化剂被首次报道以来,其独有的高活性、高原子利用率的特点,在汽车尾气处理、费托合成、生物质转化等多相催化领域掀起了一场研究风暴,似乎单原子催化剂凭借其得天得厚的优势,大有一统多相催化江湖的趋势。2011年,张涛团队利用氧化铁和铂原子之间的强相互作用,成功制备出首例具有高活性和高稳定性的Pt1/FeOx催化剂,引发了国际上单原子催化剂的研究热潮。目前,已发展的单原子催化剂制备方法主要有共沉淀法、浸渍法、质量分离软着陆法、原子层沉积法等,催化剂体系也从Pt延拓到Au、Pd和Ir等贵金属。
然而,在单原子催化领域仍然存在着亟待解决的技术难题:单原子催化剂的负载量一般很低,在制备和反应过程中单原子容易发生聚集,从而影响单原子催化剂的催化性能。公开号为CN108906113A、名称为一种高负载量的贵金属单原子催化剂及其制备方法和应用的发明专利,公开了一种能够解决单原子发生聚集的问题的单原子催化剂的制备方法,其记载制得的单原子催化剂负载量高达9.8wt%,但经本申请发明人重现该发明专利,所制得的单原子催化剂负载量最高达到3.8 wt%,该结论和与该发明专利的发明人以及发明构思完全一致的公开文献“Photochemical Solid-Phase Synthesis of Platinum SingleAtoms on Nitrogen-Doped Carbon with High Loading as Bifunctional Catalystsfor Hydrogen Evolution and Oxygen Reduction Reactions,Tuanfeng Li,JingjunLiu,Ye Song,and Feng Wang”中公开的“制得的单原子催化剂负载量最高达到3.8wt%”的描述一致,因此其负载量、分散性和催化性能有待提高。
发明内容
本发明实施例的目的在于提供一种原位光还原法制备高负载量的贵金属单原子催化剂的方法,以解决现有方法制备的单原子负载量过低导致分散性和催化性能不高的问题。
本发明实施例所采用的技术方案是:原位光还原法制备高负载量的贵金属单原子催化剂的方法,按照以下步骤进行:
步骤S1、将氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体经金属盐溶液或金属碱溶液处理使其表面负载金属离子后,用去离子水和无水乙醇洗涤至弱碱性,再超声分散;
步骤S2、在步骤S1所得溶液中再加入贵金属盐溶液以及羰基化合物混合后磁力搅拌;
步骤S3、在光照条件下进行原位光还原后冷冻干燥,制备贵金属单原子催化剂。
进一步的,所述步骤S1中每0.02~3.0g的石墨烯、氧化石墨烯或三维网络氧化石墨烯载体,加入40~60ml的摩尔浓度为1~15mol/L的金属盐溶液或金属碱溶液。
进一步的,每0.02~3.0g的氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体,对应加入负载量为0.1%~12%的贵金属盐溶液,即加入的贵金属盐溶液中贵金属元素的质量为氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体质量的0.1%~12%。
进一步的,每0.02~3.0g的氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体,对应加入0.05~2.0ml羰基化合物。
进一步的,所述步骤S1中金属盐溶液或金属碱溶液为钠或钾的盐溶液或碱溶液;
所述步骤S1中金属盐溶液或金属碱溶液处理氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯的方法为水热处理、搅拌处理、回流处理中的任意一种,处理至使氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯的表面负载钠离子和钾离子。
进一步的,所述步骤S1中金属盐溶液或金属碱溶液为氯化钠溶液、氯化钾溶液、乙酸钠溶液、乙酸钾溶液、碳酸钠溶液、碳酸钾溶液、氢氧化钠溶液、氢氧化钾溶液中的任意一种。
进一步的,所述步骤S2中贵金属盐溶液为对应贵金属元素的氯化物或乙酰丙酮盐。
进一步的,所述步骤S2中羰基化合物为丙酮、乙酰丙酮、苯乙酮中的任意一种。
进一步的,所述步骤S3在惰性气氛下,在金卤灯、高压汞灯、紫外灯、氙灯的光照下进行原位光还原后冷冻干燥制备贵金属单原子催化剂,原位光还原的反应温度为5~55℃、反应时间为0.1~2h。
进一步的,所述步骤S3在太阳光下磁力搅拌,进行原位光还原后冷冻干燥制备贵金属单原子催化剂。
本发明实施例的有益效果是,提出一种原位光还原法制备高负载量的贵金属单原子催化剂的方法,以钠或钾的盐溶液或者碱溶液处理过的氧化石墨烯等作为载体,使载体表面富含钠、钾离子,以保证贵金属单原子在载体表面分散均匀;并利用简单羰基化合物辅助原位光还原技术,借助羰基化合物和贵金属形成的配位化合物的配位点作为“爪”,用这些贵金属原子和羰基化合物形成的配位化合物作为锚定位点来构造支撑,以牢固吸附和结合贵金属单原子,防止生成的单原子迁移和凝聚,获得高负载量的单分散的Pt等贵金属单原子催化剂,经制得的单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图看出其分散效果好,制得的单分散的贵金属单原子的负载量达到4.36%,可见光下最高光催化分解水产氢效率达到1325μmol∙h-1。制备方法简单、成本低、有效解决了现有方法制备的单原子负载量低导致分散性和催化性能不高的问题。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明实施例1制备得到的金单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微(HAADF-STEM)图。
图2是本发明实施例2制备得到的铂单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图3是本发明实施例3制备得到的钯单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图4是本发明实施例4制备得到的钌单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图5是本发明实施例5制备得到的金单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图6是本发明实施例6制备得到的铱单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图7是本发明实施例7制备得到的钌单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图8是本发明实施例8制备得到的铂单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图9是本发明实施例9制备得到的铂单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图10是本发明实施例10制备得到的钌单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
图11是本发明实施例11制备得到的铂单原子催化剂的球差校正的高角度环形暗场扫描透射电子显微图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
原位光还原法制备高负载量的金单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.5g氧化石墨烯经40ml的1 mol/L乙酸钠180℃水热处理12h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散0.5h;
步骤S2、在步骤S1所得溶液中再加入0.2ml乙酰丙酮、负载量为5%的二甲基(乙酰丙酮)金(III)(即二甲基(乙酰丙酮)金(III)中金元素的质量为氧化石墨烯质量的5%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启500W金卤灯,在惰性气氛光照下进行原位光还原后冷冻干燥制备金单原子催化剂,原位光还原的反应温度为35℃、反应时间为0.2h。制备得到的金单原子催化剂如图1所示,经ICP-AES法(电感耦合等离子体原子发射光谱法)测试得该金单原子催化剂的负载量为3.95%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该金单原子催化剂在可见光下最高光催化分解水产氢效率可达到6μmol∙h-1。
实施例2
原位光还原法制备高负载量的铂单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.3g氮杂石墨烯经40ml的10mol/L氢氧化钾130℃水热处理18h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散0.5h;
步骤S2、在步骤S1所得溶液中再加入0.1ml丙酮、负载量为5%的氯化钯(即氯化钯中钯元素的质量为氮杂石墨烯质量的5%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启1000W高压汞灯,在惰性气氛光照下进行原位光还原后冷冻干燥,制备铂单原子催化剂,原位光还原的反应温度为20℃、反应时间为0.1h。制备得到的钯单原子催化剂如图2所示,经ICP-AES法测试得该铂单原子催化剂负载量为4.09%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该铂单原子催化剂在可见光下最高光催化分解水产氢效率可达到526 μmol∙h-1。
实施例3
原位光还原法制备高负载量的钯单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.02g氮杂石墨烯经40ml的5mol/L氢氧化钾搅拌处理8h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散1.0h;
步骤S2、在步骤S1所得溶液中再加入0.05ml丙酮、负载量为3%的氯化钯(即氯化钯中钯元素的质量为氮杂石墨烯质量的3%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启600W金卤灯,在惰性气氛光照下进行原位光还原后冷冻干燥制备钯单原子催化剂,原位光还原的反应温度为5℃、反应时间为0.4h。制备得到的钯单原子催化剂如图3所示,经ICP-AES法测试得该钯单原子催化剂负载量为1.71%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该钯单原子催化剂在可见光下最高光催化分解水产氢效率可达到265 μmol∙h-1。
实施例4
原位光还原法制备高负载量的钌单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.3g三维网络氧化石墨烯经40ml的5mol/L碳酸钠150℃水热处理12h,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散3.0h;
步骤S2、在步骤S1所得溶液中再加入0.1ml丙酮、负载量为5%的乙酰丙酮钌(即乙酰丙酮钌中钌元素的质量为三维网络氧化石墨烯质量的5%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启300W高压汞灯,在惰性气氛光照下进行原位光还原后冷冻干燥制备钌单原子催化剂,原位光还原的反应温度为35℃、反应时间为0.3h。制备得到的钌单原子催化剂如图4所示,经ICP-AES法测试得该钌单原子催化剂负载量为4.36%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该钌单原子催化剂在可见光下最高光催化分解水产氢效率可达到1325 μmol∙h-1。
实施例5
原位光还原法制备高负载量的金单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.4g氧化石墨烯经60ml的15mol/L氯化钠100℃回流处理后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9];
步骤S2、在步骤S1所得溶液中再加入0.05ml苯乙酮、负载量为3%的氯金酸(即氯金酸中金元素的质量为氧化石墨烯质量的3%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启300W氙灯,在惰性气氛光照下进行原位光还原后冷冻干燥制备金单原子催化剂,原位光还原的反应温度为55℃、反应时间为2.0h。制备得到的金单原子催化剂如图5所示,经ICP-AES法测试得该金单原子催化剂负载量为1.15%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该金单原子催化剂在可见光下最高光催化分解水产氢效率可达到4 μmol∙h-1。
实施例6
原位光还原法制备高负载量的铱单原子催化剂的方法,按照以下步骤进行:
步骤S1、将1.0g三维网络氧化石墨烯经40ml的2mol/L氢氧化钠160℃水热处理10h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散0.2h;
步骤S2、在步骤S1所得溶液中再加入0.5ml丙酮、负载量为1.5%的乙酰丙酮铱(即乙酰丙酮铱中铱元素的质量为三维网络氧化石墨烯质量的1.5%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启1000W高压汞灯,在惰性气氛光照下进行原位光还原后冷冻干燥制备铱单原子催化剂,原位光还原的反应温度为20℃、反应时间为0.1h。制备得到的铱单原子催化剂如图6所示,经ICP-AES法测试得该铱单原子催化剂负载量为1.28%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该铱单原子催化剂在可见光下最高光催化分解水产氢效率可达到10 μmol∙h-1。
实施例7
原位光还原法制备高负载量的铱单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.3g氧化石墨烯经60ml的10mol/L氢氧化钠100℃回流处理8h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散0.5 h;
步骤S2、在步骤S1所得溶液中再加入1.0ml丙酮、负载量为0.1%的三氯化钌(即三氯化钌中钌元素的质量为氧化石墨烯质量的0.1%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启300金卤灯,在惰性气氛光照下进行原位光还原后冷冻干燥制备钌单原子催化剂,原位光还原的反应温度为20℃、反应时间为0.3h。制备得到的铱单原子催化剂如图7所示,经ICP-AES法测试得该钌单原子催化剂负载量为0.09%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该钌单原子催化剂在可见光下最高光催化分解水产氢效率可达到358 μmol∙h-1。
实施例8
原位光还原法制备高负载量的铂单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.5g三维网络氧化石墨烯经40ml的5mol/L醋酸钾180℃回流处理6h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散1.0h;
步骤S2、在步骤S1所得溶液中再加入0.05ml丙酮、负载量为0.5%的氯铂酸(即氯铂酸中铂元素的质量为三维网络氧化石墨烯质量的0.5%)混合后磁力搅拌;
步骤S3、惰性气氛下,开启100W高压汞灯,在惰性气氛光照下进行原位光还原后冷冻干燥,制备铂单原子催化剂,原位光还原的反应温度为25℃、反应时间为1.0h,制备得到的铂单原子催化剂如图8所示,经ICP-AES法测试得该铂单原子催化剂负载量为0.35%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该铂单原子催化剂在可见光下最高光催化分解水产氢效率可达到153 μmol∙h-1。
实施例9
原位光还原法制备高负载量的铂单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.2g氧化石墨烯经40ml的10mol/L氢氧化钾130℃水热处理18h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散0.5h;
步骤S2、在步骤S1所得溶液中再加入2.0ml丙酮、负载量为2.0%的氯铂酸(即氯铂酸中铂元素的质量为氧化石墨烯质量的2.0%)后磁力搅拌;
步骤S3、将步骤S2所得溶液置于太阳光下磁力搅拌,进行原位光还原后冷冻干燥制备铂单原子催化剂,原位光还原的平均光强为80.3mW、平均温度为39.6℃、反应时间为6h,制备得到的铂单原子催化剂如图9所示,经ICP-AES法测试得该铂单原子催化剂负载量为0.40%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该铂单原子催化剂在可见光下最高光催化分解水产氢效率可达到20 μmol∙h-1。
实施例10
原位光还原法制备高负载量的钌单原子催化剂的方法,按照以下步骤进行:
步骤S1、将0.2g氧化石墨烯经40ml的5mol/L氢氧化钾130℃水热处理12h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散0.5h;
步骤S2、在步骤S1所得溶液中再加入0.2ml乙酰丙酮、负载量为5.0%的三氯化钌(即三氯化钌中钌元素的质量为氧化石墨烯质量的5.0%)后磁力搅拌;
步骤S3、将步骤S2所得溶液置于太阳光下磁力搅拌,进行原位光还原后冷冻干燥制备钌单原子催化剂,原位光还原的平均光强为78.2mW、平均温度为38.6℃、反应时间为12h,制备得到的钌单原子催化剂如图10所示,经ICP-AES法测试得该钌单原子催化剂负载量为1.26%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该钌单原子催化剂在可见光下最高光催化分解水产氢效率可达到35 μmol∙h-1。需要说明的是,太阳光光强越大则温度越高,对应反应时间越短,太阳光光强越小则温度越低,对应反应时间越长。
实施例11
原位光还原法制备高负载量的铂单原子催化剂的方法,按照以下步骤进行:
步骤S1、将3.0g氧化石墨烯经40ml的10mol/L氢氧化钾130℃水热处理18h后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],超声分散1.0h;
步骤S2、在步骤S1所得溶液中再加入2.0ml丙酮、负载量为12.0%的氯铂酸(即氯铂酸中铂元素的质量为氧化石墨烯质量的12.0%)后磁力搅拌;
步骤S3、惰性气氛下,开启500W金卤灯,在惰性气氛光照下进行原位光还原后冷冻干燥,制备铂单原子催化剂,原位光还原的反应温度为25℃、反应时间为1.0h,制备得到的铂单原子催化剂如图11所示,经ICP-AES法测试得该铂单原子催化剂负载量为10.38%。加入曙红Y作为光敏剂,三乙醇胺为牺牲剂,得该铂单原子催化剂在可见光下最高光催化分解水产氢效率可达到78 μmol∙h-1。
加入石墨烯等载体的质量过低或者过高,都会影响贵金属单原子催化剂的负载量和分散程度。采用钠元素、钾元素的盐溶液或碱溶液处理石墨烯等载体,使得石墨烯等载体表面富含Na+、K+,Na+、K+的存在能够改善贵金属的分散性,抑制贵金属单原子聚集,提高贵金属单原子催化剂的负载量,超声分散使得Na+、K+在石墨烯等载体分散均匀,以便于得到高分散的单原子催化剂。在此基础上,再借助羰基化合物和贵金属形成的配位化合物的配位点作为“爪”,用这些配位原子即贵金属原子和羰基化合物形成的配位化合物作为锚定位点来构造支撑,以牢固吸附和结合贵金属单原子,进一步防止生成的单原子迁移和凝聚,以获得高负载量的单分散的Pt等贵金属单原子催化剂。
现有技术要通过搅拌使金属离子充分吸附后将其过滤、洗涤、干燥、研磨一系列复杂的程序,而本发明实施例制备高分散性的贵金属单原子催化剂时,不需要进行干燥和研磨,整个反应是在水溶液中进行,方法更加简单,通过羰基化合物和贵金属间形成配位化合物,从而更有利于单原子的形成和分散。
另外,现有的原位光还原法在紫外光下才能实现,而本发明实施例在紫外灯、氙灯等光源中设下,甚至是太阳光照射条件下都可以实现,反应条件更温和,更节能。
以上所述仅为本发明的较佳实施例而已,并非用于限定本发明的保护范围。凡在本发明的精神和原则之内所作的任何修改、等同替换、改进等,均包含在本发明的保护范围内。
Claims (3)
1.原位光还原法制备高负载量的贵金属单原子催化剂的方法,其特征在于,按照以下步骤进行:
步骤S1、将氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体经金属盐溶液或金属碱溶液处理使其表面负载金属离子后,用去离子水和无水乙醇洗涤至弱碱性即pH为(7,9],再超声分散;
步骤S2、在步骤S1所得溶液中再加入贵金属盐溶液以及羰基化合物混合后磁力搅拌,羰基化合物为丙酮、乙酰丙酮、苯乙酮中的任意一种;
步骤S3、在光照条件下进行原位光还原后冷冻干燥,制备贵金属单原子催化剂;
所述步骤S3在太阳光下磁力搅拌,进行原位光还原后冷冻干燥制备贵金属单原子催化剂,或在惰性气氛下,在金卤灯、高压汞灯、紫外灯、氙灯的光照下进行原位光还原后冷冻干燥制备贵金属单原子催化剂,原位光还原的反应温度为5~55℃、反应时间为0.1~2h;
所述步骤S1中每0.3g的石墨烯、氧化石墨烯或三维网络氧化石墨烯载体,加入40ml的摩尔浓度为5mol/L的金属盐溶液或金属碱溶液;
每0.3g的氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体,对应加入负载量为5%的贵金属盐溶液,即加入的贵金属盐溶液中贵金属元素的质量为氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体质量的5%;
每0.3g的氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯载体,对应加入0.1ml羰基化合物;
所述步骤S1中金属盐溶液或金属碱溶液为钠或钾的盐溶液或碱溶液;
所述步骤S1中金属盐溶液或金属碱溶液处理氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯的方法为水热处理,处理至使氮杂石墨烯、氧化石墨烯或三维网络氧化石墨烯的表面负载钠离子和钾离子。
2.根据权利要求1所述的原位光还原法制备高负载量的贵金属单原子催化剂的方法,其特征在于,所述步骤S1中金属盐溶液或金属碱溶液为氯化钠溶液、氯化钾溶液、乙酸钠溶液、乙酸钾溶液、碳酸钠溶液、碳酸钾溶液、氢氧化钠溶液、氢氧化钾溶液中的任意一种。
3.根据权利要求1所述的原位光还原法制备高负载量的贵金属单原子催化剂的方法,其特征在于,所述步骤S2中贵金属盐溶液为对应贵金属元素的氯化物或乙酰丙酮盐。
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