CN113617365B - 一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料及其制备方法 - Google Patents
一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料及其制备方法 Download PDFInfo
- Publication number
- CN113617365B CN113617365B CN202110977411.6A CN202110977411A CN113617365B CN 113617365 B CN113617365 B CN 113617365B CN 202110977411 A CN202110977411 A CN 202110977411A CN 113617365 B CN113617365 B CN 113617365B
- Authority
- CN
- China
- Prior art keywords
- composite material
- porous
- stacking fault
- square boat
- placing
- 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.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000007547 defect Effects 0.000 claims abstract description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- 230000007847 structural defect Effects 0.000 claims abstract description 11
- 239000006104 solid solution Substances 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 42
- 239000011521 glass Substances 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001257 hydrogen Substances 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000013535 sea water Substances 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种具有堆垛层错的多孔Cd1‑xZnxS/GO复合材料及其制备方法,该复合材料是由Cd1‑xZnxS固溶体纳米晶包覆一层氧化石墨烯复合而成,而Cd1‑xZnxS固溶体纳米晶具有堆垛层错结构缺陷的多孔结构;首先将CdCl2·2.5H2O、ZnCl2,丙二酸,加热搅拌混合,形成均匀透明的液体,然后将该液体转移到方舟中,与另一个盛有升华硫的方舟一起,置于管式炉内,在氮气气氛下以1‑10℃/min的速度加热至300‑600℃,保温1‑4h,得到具有堆垛层错结构缺陷的多孔Cd1‑xZnxS/GO复合材料。该复合材料对于可见光光催化分解水(或海水)制氢和光催化吸附降解水中有机污染物都有很好的光催化活性。
Description
技术领域
本发明属于新能源光催化材料与技术领域,涉及一种具有堆垛层错的多孔Cd1- xZnxS/GO复合材料及其制备方法,具体地说,是涉及一种具有堆垛层错结构缺陷的多孔Cd1- xZnxS/GO复合材料光催化剂及其制备方法。
背景技术
由于能源和淡水的短缺,在可见光下设计具有高效稳定析氢性能的无贵金属光催化剂越来越受到人们的关注。Cd1-xZnxS固溶体因其禁带可调、是一种有前途的对可见光有响应的催化剂。不幸的是,光催化过程中易发生的光腐蚀现象影响了Cd1-xZnxS催化剂的推广应用。氧化石墨烯(GO)由于其独特的二维平面结构、优异的导电性、大比表面积和优越的耐腐蚀性使得构建GO@Cd1-xZnxS复合材料成为改善光催化活性、稳定性和电荷分离的理想策略。虽然关于GO@Cd1-xZnxS材料的合成方法已经做了大量的工作,包括水/溶剂热法、自组装法、化学气相沉积法等,但目前制备的GO@Cd1-xZnxS材料其光催化效率仍然较低而限制了其应用。另一方面,具有堆垛层错的材料能够降低表观活化能,堆垛层错形成“背靠背”肖特基电位,加速自由电荷的转移,抑制电子-空穴对的复合,显示出增强的催化活性。
设计合成一种具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料光催化剂,为高效水/海水光催分解产氢提供了新的选择,在新能源材料与技术领域具有重要的实用价值和现实意义。
发明内容:
本发明针对现有技术制备Cd1-xZnxS/GO复合材料过程复杂繁琐、需要多步合成,光催化活性低等缺点,提出了一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料及其制备方法,其特征在于所述复合材料是由Cd1-xZnxS固溶体纳米晶包覆一层氧化石墨烯复合而成,所述Cd1-xZnxS固溶体纳米晶具有堆垛层错结构缺陷的多孔结构,所述制备方法是前驱体碳化、硫化与氧化石墨烯壳层的生长和复合一步完成,具体包括下述步骤:
(1)将1-10mmol CdCl2·2.5H2O、1-10mmol ZnCl2,5-100mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在60-120℃的油浴锅中搅拌混合0.1-1h,形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入0.2-3g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以1-10℃/min的速度加热至300-600℃,保温1-4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
本发明的优点在于:该方法工艺简单,采用一步热解-硫化法制备具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。所述制备方法是Cd1-xZnxS与氧化石墨烯壳层的生长和耦合是一步完成的,氧化石墨烯壳层原位生长于Cd1-xZnxS固溶体纳米晶表面,形成分子水平的偶联界面,提高催化剂耐腐蚀,耐高温,耐酸碱性,有利于长期的光催化稳定性和有效的界面电荷转移。同时,氧化石墨烯壳层独特的二维平面结构促使电子快速迁移到表面接收H+生成H2,从而提高了析氢性能。堆垛层错形成“背靠背”肖特基电位,加速自由电荷的转移,抑制电子-空穴对的复合,有利于催化活性提高。
本发明所述方法制备的具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料的光催化效率高,对于光催化分解水(海水)制氢和光催化吸附降解水中有机污染物都有很好的光催化活性。
附图说明
图1为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料和对比例一、对比利二催化剂的XRD谱图。
图2为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料和商品GO的拉曼图谱。
图3为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料的SEM照片。
图4为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料的TEM照片(a)和HREM照片(b)
图5为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料N2吸脱附等温线(a)及孔分布曲线(b)。
图6为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料和对比例一、对比例二催化剂在水中(a)和海水中(b)的可见光光催化析氢速率图。
图7为为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料用于水中和海水中光催化析氢的循环稳定性实验。
具体实施方式
下面通过实施例对本发明作进一步详细说明:
实施例一:
(1)将5mmol CdCl2·2.5H2O、5mmol ZnCl2,50mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在90℃的油浴锅中搅拌混合0.5h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以5℃/min的速度加热至550℃,保温4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
实施例二:
(1)将6mmol CdCl2·2.5H2O、4mmol ZnCl2,50mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在90℃的油浴锅中搅拌混合0.5h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以5℃/min的速度加热至550℃,保温4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
实施例三:
(1)将4mmol CdCl2·2.5H2O、6mmol ZnCl2,50mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在90℃的油浴锅中搅拌混合0.5h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以5℃/min的速度加热至550℃,保温4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
实施例四:
(1)将5mmol CdCl2·2.5H2O、5mmol ZnCl2,30mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在80℃的油浴锅中搅拌混合1h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入1g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以5℃/min的速度加热至550℃,保温4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
实施例五:
(1)将1mmol CdCl2·2.5H2O、1mmol ZnCl2,10mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在70℃的油浴锅中搅拌混合1h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入0.2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以2℃/min的速度加热至600℃,保温2h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
实施例六:
(1)将8mmol CdCl2·2.5H2O、2mmol ZnCl2,40mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在70℃的油浴锅中搅拌混合1h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入0.2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以10℃/min的速度加热至600℃,保温3h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
实施例七:
(1)将2mmol CdCl2·2.5H2O、8mmol ZnCl2,60mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在100℃的油浴锅中搅拌混合0.5h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入0.2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以2℃/min的速度加热至400℃,保温4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
对比例一:
(1)将10mmol CdCl2·2.5H2O、50mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在90℃的油浴锅中搅拌混合0.5h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以5℃/min的速度加热至550℃,保温4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
对比例二:
(1)将10mmol ZnCl2、50mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在90℃的油浴锅中搅拌混合0.5h,,至形成均匀透明的液体;
(2)将步骤①形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入2g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以5℃/min的速度加热至550℃,保温4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
图1为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料和对比例一、对比利二催化剂的XRD谱图。由图可以看出,实施例一所述方法制备复合材料的6个衍射峰,分别对应于六方相固溶体Cd0.5Zn0.5S(JCPDS No.49-1302)的(100)、(002)、(101)、(102)、(110)和(103)晶面,表明所制备的复合材料中Cd1- xZnxS以Cd0.5Zn0.5S六方相固溶体的形式存在。对比例一催化剂的XRD谱图对应于六方CdS的衍射,对比例二催化剂的XRD谱图对应于六方ZnS的衍射。Cd0.5Zn0.5S固溶体衍射峰的位置介于六方CdS和六方ZnS的衍射峰之间。
图2为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料和商品GO的拉曼图谱。由图2可以看出,与商品GO的拉曼图谱相似,Cd0.5Zn0.5S/GO样品有氧化石墨烯结构的两个特征拉曼峰D峰和G峰,而且ID/IG比值为0.8,这是氧化石墨烯原位生长过程中引入含氧基团造成的缺陷导致的。
图3为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料的SEM照片。由图3中的SEM照片可以看出,Cd0.5Zn0.5S/GO样品为纳米颗粒聚集而成的直径约为100-300nm的微球。
图4为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料的TEM照片(a)和HREM照片(b)。从图4a的TEM照片可以看出,单个微球是由粒径为5-20nm的纳米颗粒组装而成,同时形成堆积孔结构。图4b是微球局部的HRTEM照片,在两个Cd0.5Zn0.5S纳米颗粒的边缘可以观察到几乎透明的少层氧化石墨烯层(虚线区域),其中0.37nm为氧化石墨烯的层间距,进一步证明通过本发明所述方法成功合成了有氧化石墨烯壳层包覆的Cd0.5Zn0.5S光催化剂,这有利于抑制Cd0.5Zn0.5S的光腐蚀和加速光生电荷在界面处的传输,这使光催化剂的稳定性和催化活性得到有效改善。两个Cd0.5Zn0.5S纳米颗粒的晶格条纹明显,0.33nm的晶格条纹与Cd0.5Zn0.5S的(002)晶面匹配,图中方框区域中出现了明显的堆叠层错缺陷结构,这是Cd2+离子和Zn2+离子在交换和取代过程中导致高密度周期性纤锌矿结构中出现的晶格缺陷。
图5为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料N2吸脱附等温线(a)及孔分布曲线(b)。Cd0.5Zn0.5S/GO复合材料N2吸脱附等温线具有明显的介孔结构的等温线特征,通过BET计算得到其比表面为33.83cm2/g,具有高的比表面积,图5b的孔径分布图显示,Cd0.5Zn0.5S/GO复合材料孔径分布较宽,存在丰富的孔结构,孔大小在2-100nm之间。这类多孔结构有利于Cd0.5Zn0.5S/GO复合材料暴露更多的活性位点,并且有利于加速质子传输和气体转移。
图6为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料和对比例一、对比例二催化剂在水中(a)和海水中(b)的可见光光催化析氢速率图。光照由300W氙灯(北京中教金源)提供,可见光照射时配备420nm截止滤波器。光密度为100mA·cm-2。在每次试验中,用超声波将30mg催化剂分散在100mL含有30%(vt)甲醇或0.25M Na2S·9H2O/0.35M Na2SO3作为牺牲剂的去离子水或简单过滤的天然海水中,天然海水取自中国黄海青岛海岸。混合溶液被转移到与检测系统相连的石英反应器中,抽真空15min以清除溶液中溶解的O2和CO2。通过循环冷却水将系统的温度维持在7℃。采用在线气相色谱仪(Agilent 7890A,高纯度N2为载气),每30min自动检测一次生成的氢气。从附图6中可以看出,无论是水光催化析氢还是海水光催化析氢,发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料都远高于对比例一CdS/GO和对比例二ZnS/GO的光催化析氢速率,在水中和海水中的光催化析氢速率分别为10.4mmol g- 1h-1和8.2mmol g-1h-1,具有高的光催化产氢速率,尤其是具有高的海水光催化分解产氢效率,这种高光催化活性对于氢能的开发具有重要意义。
图7为利用本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料用于水中和海水中光催化析氢的循环稳定性,用以表征所制备催化剂的循环使用稳定性。从图中可以看出,反应进行5个循环30h后,水中和海水中光催化析氢的产氢性能基本保持不变,说明本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料用于水尤其是海水的光催化产氢具有很好的稳定性。
将本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料用于对水溶液中有机染料进行光催化降解,结果表明本发明所制备的Cd0.5Zn0.5S/GO复合材料对于有机染料的光催化降解也具有很好的光催化性能,可以用于有机废水的处理。
将本发明实施例一所述方法制备的具有堆垛层错结构缺陷的多孔Cd0.5Zn0.5S/GO复合材料用于有机物小分子的光催化氧化,也具有很好的催化氧化选择性,表明本发明所制备的Cd0.5Zn0.5S/GO复合材料能用于小分子精细有机化学品的光催化反应合成。
上述实施例是本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,未背离本发明的原理与工艺过程下所作的其它任何改变、替代、简化等,均为等效的置换,都应包含在本发明的保护范围之内。
Claims (1)
1.一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料,其特征在于所述复合材料是由具有堆垛层错结构缺陷的多孔Cd1-xZnxS固溶体纳米晶包覆一层氧化石墨烯复合而成,制备方法具体包括下述步骤:
(1)将1-10mmol CdCl2·2.5H2O、1-10mmol ZnCl2,5-100mmol丙二酸,装在有盖的玻璃瓶中,加入磁子,在60-120℃的油浴锅中搅拌混合0.1-1h,形成均匀透明的液体;
(2)将步骤(1)形成的透明液体转移到瓷方舟中,置于管式炉内,另一个瓷方舟加入0.2-3g的升华硫,放入管式炉的气流上游,然后在氮气气氛下以1-10℃/min的速度加热至300-600℃,保温1-4h,得到具有堆垛层错结构缺陷的多孔Cd1-xZnxS/GO复合材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110977411.6A CN113617365B (zh) | 2021-08-24 | 2021-08-24 | 一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110977411.6A CN113617365B (zh) | 2021-08-24 | 2021-08-24 | 一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113617365A CN113617365A (zh) | 2021-11-09 |
CN113617365B true CN113617365B (zh) | 2023-08-04 |
Family
ID=78387622
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110977411.6A Active CN113617365B (zh) | 2021-08-24 | 2021-08-24 | 一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113617365B (zh) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103055899A (zh) * | 2012-12-10 | 2013-04-24 | 上海师范大学 | 介孔纳米球型ZnxCd1-xS粒子及其制备方法和应用 |
CN103316694A (zh) * | 2013-07-11 | 2013-09-25 | 吉林大学 | 一种Zn0.8Cd0.2S和石墨烯复合材料的制备方法 |
CN110102316A (zh) * | 2019-05-07 | 2019-08-09 | 东莞理工学院 | 一种多孔纳米球状硫化锌镉固溶体的制备方法 |
CN110227500A (zh) * | 2019-06-14 | 2019-09-13 | 青岛科技大学 | 一种Cd1-xZnxS-Ni/MoS2复合光催化剂及其制备方法、应用 |
CN110354867A (zh) * | 2019-07-18 | 2019-10-22 | 陕西科技大学 | 一种Zn0.2Cd0.8S/rGO光催化材料的制备方法 |
CN111662707A (zh) * | 2020-06-17 | 2020-09-15 | 武汉理工大学 | 一锅法制备Cu:ZnCdS/ZnS量子点发光材料的方法 |
-
2021
- 2021-08-24 CN CN202110977411.6A patent/CN113617365B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103055899A (zh) * | 2012-12-10 | 2013-04-24 | 上海师范大学 | 介孔纳米球型ZnxCd1-xS粒子及其制备方法和应用 |
CN103316694A (zh) * | 2013-07-11 | 2013-09-25 | 吉林大学 | 一种Zn0.8Cd0.2S和石墨烯复合材料的制备方法 |
CN110102316A (zh) * | 2019-05-07 | 2019-08-09 | 东莞理工学院 | 一种多孔纳米球状硫化锌镉固溶体的制备方法 |
CN110227500A (zh) * | 2019-06-14 | 2019-09-13 | 青岛科技大学 | 一种Cd1-xZnxS-Ni/MoS2复合光催化剂及其制备方法、应用 |
CN110354867A (zh) * | 2019-07-18 | 2019-10-22 | 陕西科技大学 | 一种Zn0.2Cd0.8S/rGO光催化材料的制备方法 |
CN111662707A (zh) * | 2020-06-17 | 2020-09-15 | 武汉理工大学 | 一锅法制备Cu:ZnCdS/ZnS量子点发光材料的方法 |
Non-Patent Citations (1)
Title |
---|
Deliang Zhang et al., .esign and in-situ synthesis of unique catalyst via embedding graphene oxide shell membrane in NiS2 for efficient hydrogen evolution.Applied Surface Science.2020,第1-6页. * |
Also Published As
Publication number | Publication date |
---|---|
CN113617365A (zh) | 2021-11-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Bi et al. | Research progress on photocatalytic reduction of CO 2 based on LDH materials | |
Xue et al. | 2D mesoporous ultrathin Cd0. 5Zn0. 5S nanosheet: fabrication mechanism and application potential for photocatalytic H2 evolution | |
Wang et al. | 3D porous ZnO–SnS p–n heterojunction for visible light driven photocatalysis | |
Huang et al. | In-situ growth of mesoporous Nb2O5 microspheres on g-C3N4 nanosheets for enhanced photocatalytic H2 evolution under visible light irradiation | |
Yang et al. | Constructing 2D/1D heterostructural BiOBr/CdS composites to promote CO2 photoreduction | |
CN112958061B (zh) | 一种氧空位促进直接Z机制介孔Cu2O/TiO2光催化剂及其制备方法 | |
CN106390986A (zh) | 一种钒酸铋/钛酸锶复合光催化剂的制备方法 | |
CN113663693A (zh) | 一种硫化铟锌-二氧化钛复合材料的制备方法及其在生产双氧水用于废水治理中的应用 | |
CN110665527A (zh) | 海胆状g-C3N4/NiAl-LDH半导体异质结的制备方法 | |
Peng et al. | Synthesis of a novel one-dimensional Bi 2 O 2 CO 3–BiOCl heterostructure and its enhanced photocatalytic activity | |
Ding et al. | Biomass porous carbon as the active site to enhance photodegradation of oxytetracycline on mesoporous gC 3 N 4 | |
Zhu et al. | Synthesis of high crystallinity g-C3N4 hollow spheres for efficient photocatalytic removal of U (VI) under visible light | |
Lin et al. | High-performance α-Bi2O3/CdS heterojunction photocatalyst: innovative design, electrochemical performance and DFT calculation | |
CN112371113A (zh) | 一种Bi2WO6-rGO可见光催化剂的制备方法和应用 | |
WO2020042125A1 (zh) | 一种铋酸锂-氧化铋光催化材料及其制备方法 | |
CN113493221B (zh) | 一种二氧化钼/二氧化钛纳米复合材料及其制备方法和应用 | |
CN113617365B (zh) | 一种具有堆垛层错的多孔Cd1-xZnxS/GO复合材料及其制备方法 | |
Yu et al. | Efficient removal of tetracycline hydrochloride through novel Fe/BiOBr/Bi2WO6 photocatalyst prepared by dual-strategy under visible-light irradiation | |
CN115228485B (zh) | 一种锌镉硫化物光催化剂及其制备方法与应用 | |
CN115025783B (zh) | 一种多铌氧簇/zif-67衍生物复合材料的合成方法及应用 | |
CN114471620B (zh) | 一种α-SnWO4/In2S3复合光催化剂 | |
CN115400785A (zh) | 一种用于丙烷芳构化的核壳结构催化剂及其制备方法和应用 | |
CN113634244B (zh) | 一种富含硫空位的高指数晶面GO@Cd1-xZnxS多面体材料及其制备方法 | |
Machabaphala et al. | The photoreduction of selenite and selenate on the surface of few layer black phosphorus and a UiO-66 p–n junction heterostructure | |
CN113578296A (zh) | 一种片层状灰色TiO2光催化材料及其制备方法 |
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 |