CN116966933A - 一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法 - Google Patents
一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法 Download PDFInfo
- Publication number
- CN116966933A CN116966933A CN202311011460.XA CN202311011460A CN116966933A CN 116966933 A CN116966933 A CN 116966933A CN 202311011460 A CN202311011460 A CN 202311011460A CN 116966933 A CN116966933 A CN 116966933A
- Authority
- CN
- China
- Prior art keywords
- uio
- preparation
- nanocrystalline
- drying
- time
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 6
- 239000002184 metal Substances 0.000 title claims description 6
- 238000005253 cladding Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 title abstract description 5
- 239000013207 UiO-66 Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000005642 Oleic acid Substances 0.000 claims abstract 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229940049964 oleate Drugs 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- ZYCMDWDFIQDPLP-UHFFFAOYSA-N hbr bromine Chemical compound Br.Br ZYCMDWDFIQDPLP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 239000002096 quantum dot Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000002159 nanocrystal Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种金属有机框架封装全无机钙钛矿的制备方法及应用,所述制备方法包括以下步骤:首先采用简单的溶剂热法制备了UiO‑66材料,然后在将制备好的UiO‑66与油酸、油胺、十八烯、BiBr3粉末混合,采用热注射法制备了UiO‑66包覆的Cs3Bi2Br9纳米晶复合材料。本发明利用UiO‑66材料的稳定性和多孔性,使钙钛矿量子点在其孔内形核结晶,既提高了Cs3Bi2Br9纳米晶的环境稳定性,又丰富了UiO‑66材料的孔结构。将制备的该复合材料用于可见光水分解应用,结果显示其H2生成速率高达1054.2 μmol·g‑1·h‑1,表现出较高的催化活性,该发明有望应用于光分解水制氢领域。
Description
技术领域
本发明涉及钙钛矿材料制备技术领域,具体涉及一种金属有机框架封装有机无机钙钛矿复合材料的制备方法。
背景技术
金属卤化物钙钛矿,比如CsPbX3(X=Cl, Br, I),因其具有可调带隙、长载流子寿命、大的吸收系数和高迁移率等优点在太阳能电池、发光二极管、光电探测器等光电领域得到了广泛的研究。考虑到这些优势,近几年金属卤化物钙钛矿已发展成一种新型的光催化材料,并取得了显著的效果。遗憾的是,铅元素固有的毒性以及这些钙钛矿材料对光、热和湿度的敏感性阻碍了这类材料的大规模生产和商业化。全无机铋基卤化物钙钛矿(Cs3Bi2X9, X =Cl, Br, I,)由于低毒性,已经成为了替代铅基卤化物钙钛矿一类引人注目的半导体材料,Bi3+有着和Pb2+相似的电子结构(6s2 6p0),并且Bi3+相对于Sn2+,Ge2+有更稳定的价态。但作为钙钛矿量子点材料,长久的物理化学稳定性也是一个致命的问题,进一步限制了其在光电和光催化中的进一步应用。为了提高钙钛矿量子点的稳定性,许多封装手段也被提了出来。比如采用聚合物和二氧化硅来进行包覆,从而防止水分和极性溶剂浸入从而提高稳定性。但是这种策略不仅导致主体材料载流子传输效率下降,也会抑制反应物与材料之间的接触。
金属有机框架(MOF)材料,也称为多孔配位聚合物,是具有周期性网状结构的三维多孔材料,是由金属离子(或金属簇)和有机配体通过配位键连接而形成。MOF材料具有比表面积大、多孔结构有序可调、高孔隙率和表面功能基团可修饰等优点,使其被广泛用于气体吸附和分离、光电、催化等领域。因此,MOFs可以作为封装钙钛矿纳米晶的一种良好模板,能够提高钙钛矿纳米晶稳定性的同时,同时避免了纳米颗粒的团聚。但同时也对MOF材料本身提出了要求,比如其稳定性要不受水分、温度和环境湿度等因素的影响。
综上,致力于实现金属有机框架材料对钙钛矿纳米晶进行包覆的研究,是目前材料研究的形势所需,也是为了实现在催化领域的潜在应用。
发明内容
为了解决现有技术存在的问题,我们发明了一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,保证了绿色无毒材料的同时还提高了钙钛矿纳米晶的稳定性。本发明分成两步来实现对钙钛矿纳米晶的包覆,具体包括如下步骤:
(1)金属有机框架UiO-66的制备:将0.2330 g氯化锆、对苯二甲酸溶于50 mL DMF、6 mL乙酸、0.5 mL去离子水中,在密封条件下加热搅拌,然后冷却至室温。将溶液用DMF和甲醇的混和溶液离心洗涤三次,最后烘干收集粉末。
(2)制备油酸铯前驱体:将1.628 g Cs2CO3、5 mL OA和20 mL ODE装入到100 mL三颈烧瓶中,在120 ℃ 和N2气氛下干燥60分钟,然后继续升温到150 ℃,直至所有的Cs2CO3充分反应。
(3)Cs3Bi2Br9@UiO-66复合材料的制备:将0.1687 g BiBr3、1 mL OA、1 mL OLA、10mL ODE、0.05 mL HBr和0.25 g的UiO-66装入到100 mL三颈烧瓶中,在120 ℃下真空下干燥60分钟,然后继续升温到200 ℃。此时,在剧烈搅拌下快速注入0.8 mL Cs-OA,计时5秒后,将反应混合溶液通过冰水浴迅速冷却至50 ℃以下。通过离心洗涤获得沉淀,最后放入烘箱中干燥得到Cs3Bi2Br9@UiO-66粉末。
进一步的,步骤(1)中所述加热温度为120 ℃,时间为3 h。所述DMF和甲醇的混和溶液二者比例为1:1。
进一步的,步骤(1)中所述离心条件为速度10000 r/min,离心时间5 min,所述干燥时间为12 h,干燥温度为60 ℃。
进一步的,步骤(2)中Cs2CO3充分反应的现象是溶液呈透明的金黄色。
进一步的,步骤(3)中所述洗涤有机溶剂使用的是正己烷,洗涤次数为三次。所述离心条件为速度为7000 r/min,离心时间为5 min,所述干燥时间为12 h,干燥温度为60℃。
与现有的技术相比,本发明具有以下有益效果:
为了解决金属卤化物钙钛矿纳米晶的毒性和稳定性问题,本发明合成了无铅Cs3Bi2Br9纳米晶,具有制备工艺简单和成本低廉等特点。本发明还利用了稳定性良好的多孔晶体材料UiO-66作为模板封装Cs3Bi2Br9纳米晶,借助于UiO-66材料的比表面积和多孔性,通过原位生长的方法使Cs3Bi2Br9纳米晶在其内部形核结晶。既保证了纳米晶的稳定性,也避免了因团聚而引起的光生载流子传输效率低等问题。最后将复合材料用于光催化二氧化碳还原,实现了高附加值有机物的制备和生产,在光催化领域具有广阔的应用前景。
附图说明
图1是实施例1制备的UiO-66材料的XRD图谱。
图2是实施例2制备的Cs3Bi2Br9@UiO-66复合材料的XRD图谱。
图3是实施例2制备的Cs3Bi2Br9@UiO-66复合材料的TEM图谱。
图4是实施例1和例2制备的UiO-66材料和Cs3Bi2Br9@UiO-66复合材料的吸收光谱。
图5是为实施例1和对实施例2所制备的材料在可见光辐射下的光解水产氢生成速率对比图。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并
不限于所述内容。
实施例1:一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,具体步骤如下:
将0.2330 g氯化锆、对苯二甲酸溶于50 mL DMF、6 mL乙酸、0.5 mL去离子水中,在密封条件下120 ℃加热搅拌3 h,然后冷却至室温。将获得的溶液用DMF和甲醇(二者比例为1:1)的混和溶液离心洗涤三次,离心速度为1000 rpm,时间为5 min。最后放入烘箱60 ℃烘干12 h收集粉末。
实施例2:一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,具体步骤如下:
(1)制备油酸铯前驱体:将1.628 g Cs2CO3、5 mL OA和20 mL ODE装入到100 mL三颈烧瓶中,在120 ℃和N2气氛下干燥60分钟,然后继续升温到150 ℃,直至所有的Cs2CO3充分反应,此时溶液呈透明的金黄色。
(2)Cs3Bi2Br9@UiO-66复合材料的制备:将0.1687 g BiBr3、1 mL OA、1 mL OLA、10mL ODE、0.05 mL HBr和0.25 g的UiO-66装入到100 mL三颈烧瓶中,在120 ℃下真空下干燥60分钟,然后继续升温到200 ℃。此时,在剧烈搅拌下快速注入0.8 mL Cs-OA,计时5秒后,将反应混合溶液通过冰水浴迅速冷却至50 ℃以下。将离心收集到的沉淀用正己烷洗涤三次(离心速度为7000 r/min,时间为5 min,),最后放入烘箱中60 ℃干燥12 h得到Cs3Bi2Br9@UiO-66粉末。
图1是实施例1合成的纯相UiO-66材料的XRD图谱,从图中可以看出,UiO-66结晶性良好,有较强的衍射强度,且与模拟的衍射峰完整对应,说明成功合成了UiO-66材料。
图2是实施例2合成的Cs3Bi2Br9@UiO-66复合材料的XRD图谱,可以看出在复合材料的衍射峰与模拟的UiO-66和Cs3Bi2Br9标准卡片的XRD谱匹配良好,也说明了Cs3Bi2Br9的生长过程没有改变UiO-66的结构。
图3是实施例2合成的Cs3Bi2Br9@UiO-66复合材料的TEM图谱,从图中可以看出,UiO-66的八面体的形态保持良好。其中分布在UiO-66上面的小颗粒即为Cs3Bi2Br9纳米晶,证明Cs3Bi2Br9进入了UiO-66的孔道当中。
图4是实施例2制备的Cs3Bi2Br9@UiO-66复合材料的吸收光谱,从图中可以看出,引入Cs3Bi2Br9以后,在可见光区吸收边从300 nm红移到了550 nm,红移表明合成的复合材料具有优异的光吸收能力。
图5是为实施例1和对实施例2所制备的材料在可见光辐射下的光解水产氢生成速率对比图。可以看出,Cs3Bi2Br9的产氢速率为827.6 μmol g-1 h-1,而对其进行封装以后,Cs3Bi2Br9@UiO-66复合材料的产氢速率为1054.2 μmol g-1 h-1,说明了UiO-66的引入提高了Cs3Bi2Br9的稳定性,进而也增强了产氢性能。
最后需要说明的是,以上所述仅是本发明的优选实施方式,对于本领域的技术人员以及后续的应用和生产,在没有脱离本发明专利技术原理的前提下,可作出一些改进和优化,依然视为本技术发明专利的保护范围。
Claims (5)
1.一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,其特征在于,包括如下步骤:
(1)金属有机框架UiO-66的制备:将0.2330 g氯化锆、对苯二甲酸溶于50 mL二甲基甲酰胺(DMF)、6mL乙酸、0.5mL去离子水中,在密封条件下加热搅拌,然后冷却至室温,将溶液用DMF和甲醇的混和溶液离心洗涤三次,最后烘干收集粉末;
(2)制备油酸铯前驱体(Cs-OA):将1.628 g Cs2CO3、5 mL油酸(OA)和20 mL 十八烯(ODE)装入到100 mL三颈烧瓶中,在120 ℃ 和N2气氛下干燥60分钟,然后继续升温到150℃,直至所有的Cs2CO3充分反应;
(3)Cs3Bi2Br9@UiO-66复合材料的制备:将0.1687 g BiBr3、1 mL OA、1 mL 油胺(OLA)、10 mL ODE、0.05 mL氢溴酸(HBr)和0.25 g的UiO-66装入到100 mL三颈烧瓶中,在120 ℃下真空下干燥60分钟,然后继续升温到200 ℃;此时,在剧烈搅拌下快速注入0.8 mL Cs-OA,计时5秒后,将反应混合溶液通过冰水浴迅速冷却至50 ℃以下;通过离心洗涤获得沉淀,最后放入烘箱中干燥得到Cs3Bi2Br9@UiO-66粉末。
2.根据权利要求1所述的一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,其特征在于:步骤(1)中所述加热温度为120 ℃,时间为3 h;所述DMF和甲醇的混和溶液二者比例为1:1。
3.根据权利要求1所述的一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,其特征在于:步骤(1)中所述离心条件为速度10000 r/min,离心时间5min,所述干燥时间为12 h,干燥温度为60 ℃。
4.根据权利要求1所述的一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,其特征在于:步骤(2)中Cs2CO3充分反应的现象是溶液呈透明的金黄色。
5.根据权利要求1所述的一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法,其特征在于:步骤(3)中所述洗涤有机溶剂使用的是正己烷,洗涤次数为三次;所述离心条件为速度为7000 r/min,离心时间为5 min,所述干燥时间为12 h,干燥温度为60 ℃。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311011460.XA CN116966933A (zh) | 2023-08-11 | 2023-08-11 | 一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311011460.XA CN116966933A (zh) | 2023-08-11 | 2023-08-11 | 一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116966933A true CN116966933A (zh) | 2023-10-31 |
Family
ID=88483154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311011460.XA Pending CN116966933A (zh) | 2023-08-11 | 2023-08-11 | 一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116966933A (zh) |
-
2023
- 2023-08-11 CN CN202311011460.XA patent/CN116966933A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108465489B (zh) | 一种Fe3O4@ZIF-8核壳式复合材料及其制备方法和催化应用 | |
JP6330051B2 (ja) | ナトリウム又はアンチモンによるCu(In,Ga)(S,Se)2ナノ粒子のドーピング方法 | |
CN113193126B (zh) | 一种实现无甲胺钙钛矿薄膜表面重构的制备方法及其应用 | |
CN113044876B (zh) | 一种海胆状的锌镉硫材料的制备方法 | |
CN114927623B (zh) | 有机-无机杂化双钙钛矿薄膜及太阳能电池的制备方法 | |
CN112186107A (zh) | 一种空穴传输层的锡基钙钛矿太阳能电池及其制备方法 | |
CN114700104A (zh) | 一种以石墨相氮化碳为模板的掺碳多孔微球无铅双钙钛矿复合光催化剂的制备方法 | |
CN109775749B (zh) | 一种Sn-Pb合金无机钙钛矿薄膜及其在太阳能电池中的应用 | |
CN113769728B (zh) | 一种V2O5/BiVO4/Bi2O4异质结及其制备方法和应用 | |
CN113061434A (zh) | 一种钙钛矿量子点及其制备方法与光电器件 | |
CN111111695A (zh) | 一种三维花状体锌硫镉光催化材料及其制备方法和应用 | |
CN116966933A (zh) | 一种金属有机框架包覆Cs3Bi2Br9纳米晶的制备方法 | |
CN113130678A (zh) | 一种全无机锡铅二元钙钛矿吸收材料及其制备方法 | |
CN112522776A (zh) | 一种连续制备钙钛矿光伏单晶薄膜复合材料的方法 | |
CN109880112B (zh) | 原位定向排列一维结构zif-67及其制备方法 | |
KR101307994B1 (ko) | 광흡수 나노입자 전구체, 상기 전구체 제조방법, 상기 전구체를 이용한 고품질광흡수 나노입자 및 상기 나노입자 제조방법 | |
Yang et al. | Perovskite Colloidal Nanocrystal Solar Cells: Current Advances, Challenges and Future Perspectives | |
CN110776000B (zh) | 一种全无机钙钛矿纳米晶及其制备方法和在半导体器件上的应用 | |
CN113856732A (zh) | 一种片层花状Mn(VO3)2复合g-C3N4光催化剂及其制备方法和应用 | |
CN114471730A (zh) | NH2-MIL-101(Fe)@SNW-1复合催化剂及其制备方法和应用 | |
CN113976174A (zh) | 一种金属有机框架封装有机无机钙钛矿复合光催化材料的制备方法 | |
CN103877969B (zh) | 一种In2O3·InVO4异质结构复合物及其制备和应用方法 | |
Huang et al. | Tailoring perovskite quantum dots heterojunction nanocomposite toward photocatalytic reduction of CO2 | |
Chai et al. | The effect of bromine doping on the perovskite solar cells modified by PVP/PEG polymer blends | |
CN107359244B (zh) | 基于三维海胆状ZnO超结构阵列的钙钛矿太阳电池电子传输层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 |