CN113856763A - 一种联苯基共价有机框架载铜材料及其制备方法和光催化制氢气应用 - Google Patents
一种联苯基共价有机框架载铜材料及其制备方法和光催化制氢气应用 Download PDFInfo
- Publication number
- CN113856763A CN113856763A CN202111266667.2A CN202111266667A CN113856763A CN 113856763 A CN113856763 A CN 113856763A CN 202111266667 A CN202111266667 A CN 202111266667A CN 113856763 A CN113856763 A CN 113856763A
- Authority
- CN
- China
- Prior art keywords
- copper
- organic framework
- covalent organic
- biphenyl
- cof
- 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
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 77
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 41
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 31
- 239000004305 biphenyl Substances 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000010949 copper Substances 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims abstract description 10
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims abstract description 6
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960001553 phloroglucinol Drugs 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 4
- 235000010378 sodium ascorbate Nutrition 0.000 description 4
- 229960005055 sodium ascorbate Drugs 0.000 description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- XCBKGJWOCHSAMS-UHFFFAOYSA-L copper;dichlorocopper Chemical compound [Cu].Cl[Cu]Cl XCBKGJWOCHSAMS-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
本发明属于材料制备及催化领域,提出一种联苯基共价有机框架载铜材料及其制备方法和光催化产氢的应用。首先以三甲酰基间苯三酚和联苯胺两种单体通过溶剂热法,发生缩合反应得到联苯基共价有机框架材料(BD‑COF),然后,将二水合氯化铜与所制备的BD‑COF材料复合,最终得到联苯基共价有机框架载铜光催化材料。可实现对可见光的利用,在光催化产氢领域有一定利用价值和巨大潜力。
Description
技术领域
本发明属于材料制备领域,具体涉及一种联苯基共价有机框架载铜材料及其制备方法和光催化制氢气应用。
背景技术
面对石油等化石能源高污染及储量有限的固有缺点,近些年人们一直致力于探索更环保、高效、可再生的新型能源。氢气作为一种高能量密度的绿色能源,正好符合这些需求,因此受到了越来越多人的关注。氢气氧化燃烧产物是水,对环境无污染,但目前氢气的主要获取方式还是通过化石能源,在日益强调环保低碳的当下变得不合时宜,开发环保高效的获取氢气途径已迫在眉睫。太阳能作为取之不尽用之不竭的能源,加之其环保可持续特性被认为在驱动水分解制氢方面具有巨大潜能。
共价有机框架材料是一种由碳氢氧氮等轻质元素通过强共价键结合而成的结晶性多孔材料,具有高比表面积、高稳定性、结构可调、易于功能化等特点,近些年在催化领域得到了广泛关注。与非均相催化相比,共价有机框架材料等非均相催化具有易于回收和分离的优势,符合对于水分解催化剂的要求。然而,一般的半导体催化剂不具有高析氢活性,这是由于电子-空穴对在迁移到半导体表面进行反应之前快速复合,更何况表面反应太慢而无法有效地耗尽电荷。共价有机框架材料的另一个吸引人的特性是它们能够通过量杂原子(如 N、S 和 O)的配位键锚定单个金属原子,并表现出金属中心的独特功能,类似于均质有机金属。考虑到金属中心依赖于宽范围的可见光吸收,因此金属修饰的共价有机框架材料有望成为光化学应用材料的有吸引力的平台。非贵金属助催化剂如Cu等被发现是一种高活性、稳定和低成本的助催化剂,可以与各种光催化剂用于将水高效光催化分解为氢。
我们制备出通过席夫碱反应溶剂热法合成的联苯基共价有机框架载铜材料,光催化制氢的性能测试表明,在可见光下,以水作为溶剂,抗坏血酸钠作为电子牺牲剂的条件下,该共价有机框架光催化剂产H2效率达到17.45 mmol h-1 g-1,且具有较好的循环使用稳定性。结果表明联苯基共价有机框架载铜材料在光催化产氢领域具有重要的应用潜力。
发明内容
本发明制备出联苯基共价有机框架载铜材料并用于光催化产氢气。铜可代替铂、银等贵金属在催化中的使用,并可以达到与贵金属铂催化产氢气相当的效果,发现其在催化产氢方面具有一定应用价值。
为实现上述发明目的,本发明采用如下技术方案:
所述Cu@BD-COF催化剂的制备方法:
一种联苯基共价有机框架载铜材料(Cu@BD-COF)中联苯基共价有机框架是在三甲酰基间苯三酚和联苯胺(BD)两种单体通过缩合反应合成的。将质量比为1:100~1:10的CuCl2·2H2O和上述联苯基共价有机框架材料加入无水乙醇中,在25℃下搅拌3~6h,然后旋蒸除去溶剂并收集催化剂,并在60℃真空干燥过夜,得到联苯基共价有机框架载铜材料(Cu-BD-COF)。
上述联苯基共价有机框架载铜材料(Cu-BD-COF)在光催化产氢中的应用:
称取10 mg Cu-BD-COF,加入0.5g抗坏血酸钠及50mL水,超声15分钟后将其投入特制石英玻璃光催化反应器。反应器抽真空后,然后反应器在装有λ≥420nm截止滤光片的氙灯下照射。在光催化反应过程中需要不停搅拌,反应器中的气体每隔1h,用气相色谱仪测定H2的产率。根据检测到的H2的含量来说明Cu-BD-COF的光催化性能。
联苯基共价有机框在可见光范围内具有很好的光吸收,且能带结构满足光解水产氢的条件,其优异的光吸收能力可作为光捕获剂,吸收能量后激发光生电子和光生空穴。光生电子传导到锚定在BD-COF中的Cu上,Cu作为催化反应的活性位点,将吸附的质子还原为氢气。光生空穴被抗坏血酸钠消耗,有效防止了光生电子和空穴的复合。
上述技术方案中的一个或一些技术方案具有如下优势:
(1)负载铜源为商业化的无机铜盐氯化铜,负载过程简便易行,只需要物理混合搅拌并旋蒸收集,可实现大规模应用,并且用量很少,成本较低。
(2)采用联苯基共价有机框架载铜材料作为光催化产氢的催化剂,相较于其他基于共价有机框架的光催化材料具有较高的光解水产氢效率。
(3)本联苯基共价有机框架载铜材料容易回收且干燥后可重复使用,多次循环后催化剂性能没有明显下降。
(4)本发明的联苯基共价有机框架属于β-酮烯胺COF可在强酸强碱及不同溶剂中保持化学稳定性,孔径大小也有利于水分子的进出及参与反应。联苯基共价有机框架载铜材料中,铜通过与联苯基共价有机框架的氧原子配位形成共价偶联,利于接受光生电子,铜具有优良的导电性质,从而促进还原反应的发生。因此本联苯基共价有机框架载铜材料具有较高的光催化产氢效率。
附图说明
图1:实施例1中制备的Cu-BD-COF合成示意图;
图2:实施例1中利用溶剂热法制备的BD-COF以及Cu-BD-COF的X射线粉末衍射图;图中3.5°处的特征衍射峰表明BD-COF以及Cu-BD-COF的成功合成;
图3:实施例1中利用溶剂热法制备的BD-COF以及Cu-BD-COF的傅里叶变换红外光谱图;C=N、C-N特征吸收峰的出现表明材料的成功合成,且负载铜后其结构未被破坏;
图4:实施例1中Cu-BD-COF的SEM图;图中可以看到Cu-BD-COF是表面覆盖纳米大小颗粒的海参状形貌;
图5:实施例1中制备的Cu-BD-COF的光催化产氢量随时间变化图;可以看出Cu-BD-COF具有光催化水产氢性能;
图6:实施例1中制备的Cu-BD-COF的光催化产氢循环性能图;每4小时一次循环,可以看出Cu-BD-COF具有好的循环使用性能。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图即实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用于解释本发明,并不用于限定本发明。
实施例1
将三甲酰基间苯三酚()和联苯胺(BD)用溶剂热法合成BD-COF。之后将100mg BD-COF、 8mgCuCl2·H2O加入15mL的试管中,并加入5mL乙醇分散,在25℃下以600rpm的速度搅拌3小时。然后通过旋蒸除去乙醇,并将试管内剩余粉末收集,在60℃下真空干燥过夜,得到Cu-BD-COF。如图1、2、3、4所示分别为制备的Cu-BD-COF的合成示意图、Cu-BD-COF的X射线粉末衍射图、Cu-BD-COF的傅里叶变换红外光谱图以及Cu-BD-COF的SEM图。
实施例2
将三甲酰基间苯三酚和联苯胺(BD)用溶剂热法合成BD-COF。之后将100mg BD-COF、 3mgCuCl2·H2O加入15mL的试管中,并加入5mL乙醇分散,在25℃下以600rpm的速度搅拌3小时。然后通过旋蒸除去乙醇,并将试管内剩余粉末收集,在60℃下真空干燥过夜,得到Cu-BD-COF。
实施例3
将三甲酰基间苯三酚和联苯胺(BD)用溶剂热法合成BD-COF。之后将100mg BD-COF、 8mgCuCl2·H2O加入15mL的试管中,并加入5mL乙醇分散,在25℃下以600rpm的速度搅拌5小时。然后通过旋蒸除去乙醇,并将试管内剩余粉末收集,在60℃下真空干燥过夜,得到Cu-BD-COF。
应用例1
称取10 mg Cu-BD-COF,加入0.5g抗坏血酸钠及50mL水,超声15分钟后将其投入特制石英玻璃光催化反应器。反应器抽真空后,然后反应器在具有λ≥420nm截止滤光片的氙灯下照射。在光催化反应过程中需要不断搅拌,反应器中的气体每隔1h,用气相色谱法测定H2的产率。根据检测到的H2的含量来说明Cu-BD-COF的光催化性能。
图5是制备的联苯基共价有机框架载铜材料的在可见光下光催化产氢量随时间的变化速率图,由图可知,在所述负载铜的共价有机框架光催化剂产生H2的速率平均值为17.45 mmol h-1 g-1,说明本发明所制备的联苯基共价有机框架载铜材料确实具有良好的光催化水分解产H2活性。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (7)
1.一种联苯基共价有机框架载铜材料的制备方法,其特征在于以三甲酰基间苯三酚和联苯胺为原料通过缩合反应得到共价有机框架材料与铜源复合,在溶剂中搅拌旋蒸收集并真空干燥,最终得到联苯基共价有机框架载铜材料。
2.根据权利要求1所述的联苯基共价有机框架载铜材料的制备方法,其特征在于:所述铜源为二水合氯化铜。
3.根据权利要求2所述的联苯基共价有机框架载铜材料的制备方法,其特征在于:所述二水合氯化铜和共价有机框架材料的质量比为1:100-1:10。
4.根据权利要求1所述的联苯基共价有机框架载铜材料的制备方法,其特征在于:所述溶剂为乙醇。
5.根据权利要求1所述的联苯基共价有机框架载铜材料的制备方法,其特征在于:所述搅拌具体为:在25℃下搅拌3~6h。
6.一种如权利要求1-5任一项所述制备方法制得的联苯基共价有机框架载铜材料。
7.一种如权利要求6所述的联苯基共价有机框架载铜材料在光催化制氢气中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111266667.2A CN113856763B (zh) | 2021-10-29 | 2021-10-29 | 一种联苯基共价有机框架载铜材料及其制备方法和光催化制氢气应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111266667.2A CN113856763B (zh) | 2021-10-29 | 2021-10-29 | 一种联苯基共价有机框架载铜材料及其制备方法和光催化制氢气应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113856763A true CN113856763A (zh) | 2021-12-31 |
CN113856763B CN113856763B (zh) | 2023-02-28 |
Family
ID=78985728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111266667.2A Active CN113856763B (zh) | 2021-10-29 | 2021-10-29 | 一种联苯基共价有机框架载铜材料及其制备方法和光催化制氢气应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113856763B (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170130349A1 (en) * | 2015-11-10 | 2017-05-11 | Indian Educational and Research Institute | Covalent organic frameworks as porous supports for non-noble metal based water splitting electrocatalysts |
CN107175053A (zh) * | 2017-05-27 | 2017-09-19 | 福州大学 | 一种核壳结构的共价有机骨架复合微球的制备方法 |
CN108794756A (zh) * | 2018-06-28 | 2018-11-13 | 福州大学 | 一种镍离子修饰的共价有机框架材料的制备方法及其应用 |
CN111871376A (zh) * | 2020-06-15 | 2020-11-03 | 南昌大学 | 一种共价有机框架多孔纳米复合材料的制备及应用 |
CN113265061A (zh) * | 2021-05-19 | 2021-08-17 | 重庆工商大学 | 一种Ru/Cu-BTC金属有机框架材料的制备方法及应用 |
-
2021
- 2021-10-29 CN CN202111266667.2A patent/CN113856763B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170130349A1 (en) * | 2015-11-10 | 2017-05-11 | Indian Educational and Research Institute | Covalent organic frameworks as porous supports for non-noble metal based water splitting electrocatalysts |
CN107175053A (zh) * | 2017-05-27 | 2017-09-19 | 福州大学 | 一种核壳结构的共价有机骨架复合微球的制备方法 |
CN108794756A (zh) * | 2018-06-28 | 2018-11-13 | 福州大学 | 一种镍离子修饰的共价有机框架材料的制备方法及其应用 |
CN111871376A (zh) * | 2020-06-15 | 2020-11-03 | 南昌大学 | 一种共价有机框架多孔纳米复合材料的制备及应用 |
CN113265061A (zh) * | 2021-05-19 | 2021-08-17 | 重庆工商大学 | 一种Ru/Cu-BTC金属有机框架材料的制备方法及应用 |
Non-Patent Citations (3)
Title |
---|
YING ZANG ET AL.: "Prefabricated covalent organic framework nanosheets with double vacancies: anchoring Cu for highly efficient photocatalytic H2 evolution", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
ZHIYUE DONG ET AL.: "Covalent organic framework nanorods bearing single Cu sites for efficient photocatalysis", 《CHEMICAL ENGINEERING JOURNAL》 * |
李丽等: "共价有机框架材料在光催化领域中的应用", 《高等学校化学学报》 * |
Also Published As
Publication number | Publication date |
---|---|
CN113856763B (zh) | 2023-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109999866B (zh) | 一维硫化镉/硫化铜/磷化镍光催化剂及其制备方法与应用 | |
CN111203231B (zh) | 硫化铟锌/钒酸铋复合材料及其制备方法和应用 | |
CN113019459B (zh) | 一种二氧化钛卟啉基共价有机框架复合材料及其制备方法和应用 | |
CN111013608A (zh) | 一种金属镍修饰的硫铟锌光催化剂及其制备方法与应用 | |
CN112495421B (zh) | 一种氮掺杂碳量子点修饰富氮石墨型氮化碳光催化剂的制备方法 | |
CN113058617B (zh) | 一种光催化剂及其制备方法和应用 | |
CN111957354A (zh) | 一种氧缺陷二氧化钛/TpPa-1-COF异质结光催化剂的制备方法 | |
CN114177940B (zh) | 一种单原子Cu锚定共价有机框架材料的制备及其应用 | |
CN114534783B (zh) | 一种制备单原子Pt嵌入共价有机框架的光催化剂的方法及其应用 | |
CN114797936B (zh) | 一种co2还原催化剂、应用及其制备方法 | |
CN114160169B (zh) | 一种共价有机框架材料封装钼硫团簇的制备方法及其应用 | |
JP4528944B2 (ja) | 硝酸イオン存在下の酸化的雰囲気においてIr酸化物系助触媒を担持させた光触媒およびその製造方法 | |
CN114591477A (zh) | 亚胺连接的二苯并噻吩砜基共价有机框架材料的制备和应用 | |
Yin et al. | Enhanced charge transfer and photocatalytic carbon dioxide reduction of copper sulphide@ cerium dioxide pn heterojunction hollow cubes | |
CN113856763B (zh) | 一种联苯基共价有机框架载铜材料及其制备方法和光催化制氢气应用 | |
CN116440955A (zh) | 卟啉基mof/硫铟锌异质结复合光催化剂及其制备与应用 | |
CN115286757B (zh) | 基于多氮烯烃连接的共价有机框架材料及其制备方法和应用 | |
CN116120505A (zh) | 一类含卤素芘基共价有机框架聚合物光催化剂及其制备方法和应用 | |
CN115652363A (zh) | 一种用于催化产氨的铁氮碳单原子催化剂的制备和应用 | |
CN115403782A (zh) | 一种含硫、氮基团的二维金属有机框架材料、共轭双金属有机框架材料及其制备方法和应用 | |
CN113398968A (zh) | 一种MOF衍生的TiO2/多孔g-C3N4复合光催化剂及其制备方法和应用 | |
CN113398997A (zh) | 一种铂掺杂超薄Zr-MOFs纳米薄层复合光催化剂及其制备方法和应用 | |
CN116422378B (zh) | 一种Cu2O-CuXbpy复合材料CO2光还原催化剂的制备方法和应用 | |
CN112958124B (zh) | 一种铟掺杂碳化钼纳米花核壳结构光催化剂及其制备和应用 | |
CN115521441B (zh) | 一种共轭微孔聚合物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 |