CN105964278A - 一种一维Zn1-xCoxS固溶体与碳纳米复合光催化剂及其制备方法 - Google Patents
一种一维Zn1-xCoxS固溶体与碳纳米复合光催化剂及其制备方法 Download PDFInfo
- Publication number
- CN105964278A CN105964278A CN201610311075.0A CN201610311075A CN105964278A CN 105964278 A CN105964278 A CN 105964278A CN 201610311075 A CN201610311075 A CN 201610311075A CN 105964278 A CN105964278 A CN 105964278A
- Authority
- CN
- China
- Prior art keywords
- solid solution
- preparation
- catalyst
- dimensional
- zinc
- 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 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 239000006104 solid solution Substances 0.000 title claims abstract description 31
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009830 intercalation Methods 0.000 claims abstract description 10
- 230000002687 intercalation Effects 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229960001860 salicylate Drugs 0.000 claims description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 8
- 229960004025 sodium salicylate Drugs 0.000 claims description 8
- CPOXHKWVHTWUGL-UHFFFAOYSA-J zinc;cobalt(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Zn+2] CPOXHKWVHTWUGL-UHFFFAOYSA-J 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 claims description 2
- 229960003629 potassium salicylate Drugs 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract 2
- 229960004889 salicylic acid Drugs 0.000 abstract 2
- KIJJUKCMZVPHFU-UHFFFAOYSA-L [Co](O)O.[Zn] Chemical compound [Co](O)O.[Zn] KIJJUKCMZVPHFU-UHFFFAOYSA-L 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FQGXNCRXCKAZLZ-UHFFFAOYSA-J zinc;nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ni+2].[Zn+2] FQGXNCRXCKAZLZ-UHFFFAOYSA-J 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- Toxicology (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种一维Zn1‑xCoxS固溶体与碳纳米复合光催化剂及其制备方法。本发明是以锌盐、钴盐和水杨酸盐为原料,首先共沉淀法合成水杨酸根插层的层状双金属氢氧化锌钴前驱体,以该前驱体与H2S气体经气固相反应后,再在惰性气体氛围中焙烧得到一维Zn1‑xCoxS固溶体与碳纳米复合光催化剂。该催化剂稳定性高,并具有较大的比表面积,其中固溶体纳米粒子尺寸均匀,粒径较小,为3‑5nm。用石墨碳来作为基底,维持了材料的一维特性,显著提高了材料的导电性和稳定性。该催化剂具有较强的光催化能力,尤其在可见光下具有显著的光催化活性。与常见的合成方法相比,无需引入模板剂、修饰剂,绿色经济,并且原料易得,成本低廉,适合大规模生产。
Description
技术领域
本发明属于光催化剂制备技术领域,具体涉及一种一维的Zn1-xCoxS固溶体与碳纳米复合光催化剂及其制备方法。
背景技术
ZnS是具有直接宽带隙的半导体材料,有较大的禁带宽度(3.66eV)。作为一种过渡金属硫化物,ZnS具有许多优异的特性,其中光催化是其独特的性能之一。ZnS在紫外光照射激发及牺牲剂存在的情况下具有很强的光催化活性,但是ZnS的宽禁带限制了其对可见光的吸收。由于固溶体能同时调节半导体的价带和导带位置,由其它金属阳离子置换ZnS中的锌离子所形成固溶体纳米粒子,可以缩小其禁带宽度,扩大其对可见光的吸收,从而增强光催化能力。
碳材料(如CNT、CNF、graphene)具有独特的结构和优异的性能,如大的比表面积,良好的化学稳定性和热稳定性,较大的机械强度和电子传输能力等,是一种具有良好发展前景的催化剂载体。将固溶体和碳材料复合在一起,则可以进一步改善其优异的性能。现有的制备方法需用高温高压,条件苛刻,并且由于团聚所导致的大的粒子尺寸(约为100nm),限制了其光催化活性的进一步提高。
发明内容
本发明的目的在于提供一种一维Zn1-xCoxS固溶体与碳纳米复合光催化剂及其制备方法。
本发明是以锌盐、钴盐和水杨酸盐为原料,首先共沉淀法合成水杨酸根插层的层状双金属氢氧化锌钴前驱体,以该前驱体与H2S气体经气固相反应后,再在惰性气体氛围中焙烧得到一维Zn1-xCoxS固溶体与碳纳米复合光催化剂。
本发明合成的一维Zn1-xCoxS固溶体与碳纳米复合光催化剂为一维的纳米棒状,直径为40-60nm,Zn1-xCoxS固溶体均匀的分散在石墨碳基底内;该催化剂的比表面积为96-165m2/g;所述的Zn1-xCoxS固溶体由部分的Co2+置换ZnS晶格中的Zn2+形成,粒子尺寸为3-5nm,其中Co2+占(Zn2++Co2+)摩尔百分比为5-30%,即x=5-30%。
本发明所述的一维Zn1-xCoxS固溶体与碳纳米复合光催化剂的制备方法,其具体步骤如下:
1)将总浓度为0.1-0.5mol·L-1的无机锌盐和金属钴盐的混合溶液与浓度为0.2-2.5mol·L-1的水杨酸盐溶液在四口烧瓶中均匀混合,无机锌盐和金属钴盐的摩尔数之和与水杨酸盐的摩尔数之比为1:2-5,其中锌离子和钴离子的摩尔比为10:0.5-3;然后使用浓度为0.1-0.5mol·L-1的碱溶液调节混合溶液的pH值为5-8,25-100℃下反应12-36h,产物用去离子水离心洗涤,干燥,得到水杨酸根插层的一维双金属层状氢氧化锌钴前驱体;
2)将制得的水杨酸根插层的一维双金属层状氢氧化锌钴前驱体放置于广口瓶中,以5-100mL·min-1的流速向瓶内通入H2S气体反应1-30分钟,待反应完全后,于管式炉中300-400℃温度下惰性气体氛围中焙烧0.5-8h,得到一维Zn1-xCoxS固溶体与碳纳米复合光催化剂。
步骤1)中所述的无机锌盐选自硝酸锌、氯化锌、硫酸锌中的一种或几种。
步骤1)中所述的金属钴盐选自Co(NO3)2、CoCl2、CoSO4中的一种或几种。
步骤1)中所述的水杨酸盐为水杨酸钠、水杨酸钾中的一种或两种。
步骤1)中所述的碱溶液为NaOH、KOH、或尿素溶液。
步骤2)中所述的惰性气体为氮气、氩气。
本发明的有益效果在于:本发明以有机小分子为碳源,利用原位固相法制备了新型的一维Zn1-xCoxS固溶体与碳纳米复合光催化剂。该催化剂稳定性高,并具有较大的比表面积,其中固溶体纳米粒子尺寸均匀,粒径较小,为3-5nm。用石墨碳来作为基底,维持了材料的一维特性,显著提高了材料的导电性和稳定性。该催化剂具有较强的光催化能力,尤其在可见光下具有显著的光催化活性。与常见的合成方法相比,无需引入模板剂、修饰剂,本发明方法步骤简单可控,绿色经济,并且原料易得,成本低廉,工艺简单,适合大规模生产。
附图说明
图1是400℃下实施例1制得的一维Zn0.8Co0.2S/C纳米复合光催化剂和ZnS/C的XRD图片,上方曲线为Zn0.8Co0.2S/C,下面的曲线为ZnS/C。
图2是实施例1制得的一维Zn0.8Co0.2S/C纳米复合光催化剂和ZnS/C的(111)晶面XRD图片,上方曲线为Zn0.8Co0.2S/C,下面的曲线为ZnS/C。
图3是实施例1制得的一维Zn0.8Co0.2S/碳纳米复合光催化剂的SEM图片(上)和HRTEM图片(下)。
图4是实施例1制得的一维Zn0.8Co0.2S/碳纳米复合光催化剂的拉曼谱图。
图5是实施例1制得的一维Zn0.8Co0.2S/碳纳米复合光催化剂降解亚甲基蓝溶液的浓度变化。
图6为是实施例1制得的一维Zn0.8Co0.2S/碳纳米复合光催化剂的SEM图片。
具体实施方式
实施例1
1)称取4.7598g Zn(NO3)2·6H2O、1.1641g Co(NO3)2·6H2O和6.4044g水杨酸钠,室温下将Zn(NO3)2·6H2O和Co(NO3)2·6H2O溶于100mL去离子水中配制成混合盐溶液,将水杨酸钠溶于150mL去离子水中配制成盐溶液,将配制好的两种盐溶液倒入四口烧瓶中,并开始用电动搅拌器匀速转动,使盐溶液混合均匀;
2)称取2g NaOH溶于100mL去离子水中配制成碱液,以2滴/s的滴速向混合盐溶液中滴加,溶液中开始有粉红色沉淀逐渐析出,调节溶液的pH值为6.8,升高温度至90℃,在此温度下反应24小时,反应结束后,将沉淀物取出,离心分离,用去离子水洗涤3次,产物在50℃下烘干6小时,得到水杨酸根插层的一维双金属层状氢氧化锌钴前驱体。
3)将步骤2)制得的水杨酸根插层的一维层状前驱体放置于反应装置中,室温下通入流速为20mL·min-1的H2S气体反应10分钟,然后通入N2气体1小时除去残余的H2S气体。
4)将步骤3)制得的样品放置于管式炉中,在400℃条件下,在氮气气氛下焙烧2h得到钴掺杂的一维Zn0.8Co0.2S固溶体与碳纳米复合光催化剂。
5)称取步骤4)制得的光催化剂30mg分散到盛有50mL 20mg/L的亚甲基蓝溶液的双层光催化反应容器中,暗箱中搅拌30min,使其达到吸脱附平衡。在持续搅拌的条件下,将光催化反应器放置于可见光灯下,并通入循环水保持恒温。然后每隔半个小时移取2ml溶液,用紫外分光光度计测定亚甲基蓝溶液的浓度变化,来评价该纳米复合光催化剂的光催化活性。
从图1可以看出,XRD衍射峰除了立方晶相ZnS(111)、(220)、(311)的三个明显晶面衍射峰外,还有石墨碳(120)的衍射峰,没有其他杂相峰,且掺入Co2+ 后仍保持ZnS的立方晶相结构,说明该纳米复合材料主要由单相固溶体纳米粒子和碳组成。
从图2中(111)晶面衍射峰的偏移可以明显看出ZnS中Co2+置换了Zn2+,是由于Co2+的离子半径比Zn2+ 的离子半径稍小,会导致晶格常数的稍微变化。
从图3(上)可以看出,Zn0.8Co0.2S固溶体与碳纳米复合光催化剂为一维纳米棒状结构,表面粗糙,直径约为50nm,测其比表面积为162.326m2/g。从图3(下)HRTEM照片可以看出固溶体纳米粒子均匀的分布在碳基底内,结合谢乐公式和(111)晶面的半峰宽,计算所得纳米粒子的尺寸为4.12nm。层间距为0.308nm,略小于ZnS(JCPDF 05-0566)的0.312nm。这是由于离子半径稍小的Co2+离子置换了Zn2+离子,导致了层间距的减小,与XRD结果相一致。
从图4拉曼谱图可以看出,Zn0.8Co0.2S固溶体与碳纳米复合光催化剂在1590cm-1处有一处宽峰出现而在2900cm-1处有突起,1590cm-1处为石墨碳G峰的特征峰,出峰宽且强度不高,证明有少量石墨层出现,2900cm-1处为石墨碳的2D峰。
从图5可以看出,Zn0.8Co0.2S固溶体与碳纳米复合光催化剂与在相同条件下制得的纯ZnS/碳纳米复合光催化剂相比,于可见光下降解染料亚甲基蓝的速率明显增大,4小时后降解率达到96.55%,几乎降解完全,光催化效果显著。
实施例2
1)称取5.3548g Zn(NO3)2·6H2O、0.5821g Co(NO3)2·6H2O和9.6066g水杨酸钠,室温下将Zn(NO3)2·6H2O和Co(NO3)2·6H2O溶于100mL去离子水中配制成混合盐溶液,将水杨酸钠溶于150mL去离子水中配制成盐溶液,将配制好的两种盐溶液倒入四口烧瓶中,并开始用电动搅拌器匀速转动,使盐溶液混合均匀;
2)称取2g NaOH溶于100mL去离子水中配制成碱液,以2滴/s的滴速向混合盐溶液中滴加,溶液中开始有粉红色沉淀逐渐析出,调节溶液的pH值为6.7,升高温度至90℃,在此温度下反应24小时,反应结束后,将沉淀物取出,离心分离,用去离子水洗涤3次,产物在50℃下烘干6小时,得到一维层状双金属氢氧化锌镍前驱体。
3)将步骤2)制得的水杨酸根插层的一维层状前驱体放置于反应装置中,室 温下通入流速为20mL·min-1的H2S气体反应10分钟,然后通入N2气体中1小时除去残余的H2S气体。
4)将步骤3)制得的样品放置于管式炉中,在300℃条件下,在氮气气氛下焙烧2h得到钴掺杂的一维Zn0.9Co0.1S固溶体与碳纳米光催化剂。
5)称取步骤4)制得的光催化剂30mg分散到盛有50mL 20mg/L的亚甲基蓝溶液的双层光催化反应容器中,暗箱中搅拌30min,使其达到吸脱附平衡。在持续搅拌的条件下,将光催化反应器放置于可见光灯下,并通入循环水保持恒温。然后每隔半个小时移取2ml溶液,用紫外分光光度计测定亚甲基蓝溶液的浓度变化,来评价该纳米复合光催化剂的光催化活性。
实施例3
1)称取4.1649g Zn(NO3)2·6H2O、1.7462g Co(NO3)2·6H2O和9.6066g水杨酸钠,室温下将Zn(NO3)2·6H2O和Co(NO3)2·6H2O溶于100mL去离子水中配制成混合盐溶液,将水杨酸钠溶于150mL去离子水中配制成盐溶液,将配制好的两种盐溶液倒入四口烧瓶中,并开始用电动搅拌器匀速转动,使盐溶液混合均匀;
2)称取2g NaOH溶于100mL去离子水中配制成碱液,以2滴/s的滴速向混合盐溶液中滴加,溶液中开始有粉红色沉淀逐渐析出,调节溶液的pH值为6.7,升高温度至90℃,在此温度下反应24小时,反应结束后,将沉淀物取出,离心分离,用去离子水洗涤3次,产物在50℃下烘干6小时,得到一维层状双金属氢氧化锌镍前驱体。
3)将步骤2)制得的水杨酸根插层的一维层状前驱体放置于反应装置中,室温下通入流速为20mL·min-1的H2S气体反应10分钟,然后通入N2气体中1小时除去残余的H2S气体。
4)将步骤3)制得的样品放置于管式炉中,在300℃条件下,在氮气气氛下焙烧2h得到钴掺杂的一维Zn0.7Co0.3S固溶体与碳纳米光催化剂。
5)称取步骤4)制得的光催化剂30mg分散到盛有50mL 20mg/L的亚甲基蓝溶液的双层光催化反应容器中,暗箱中搅拌30min,使其达到吸脱附平衡。在持续搅拌的条件下,将光催化反应器放置于可见光灯下,并通入循环水保持恒温。然后每隔半个小时移取2ml溶液,用紫外分光光度计测定亚甲基蓝溶液的浓度变化,来该评价纳米复合光催化剂的光催化活性。
Claims (7)
1.一种一维Zn1-xCoxS固溶体与碳纳米复合光催化剂,其特征在于,该催化剂为一维的纳米棒状,直径为40-60nm,Zn1-xCoxS固溶体均匀的分散在石墨碳基底内;该催化剂的比表面积为96-165m2/g;所述的Zn1-xCoxS固溶体由部分的Co2+置换ZnS晶格中的Zn2+形成,粒子尺寸为3-5nm,其中Co2+占(Zn2++Co2+)摩尔百分比为5-30%,即x=5-30%。
2.一种一维Zn1-xCoxS固溶体与碳纳米复合光催化剂的制备方法,其特征在于,其具体步骤如下:
1)将总浓度为0.1-0.5mol·L-1的无机锌盐和金属钴盐的混合溶液与浓度为0.2-2.5mol·L-1的水杨酸盐溶液在四口烧瓶中均匀混合,无机锌盐和金属钴盐的摩尔数之和与水杨酸盐的摩尔数之比为1:2-5,其中锌离子和钴离子的摩尔比为10:0.5-3;然后使用浓度为0.1-0.5mol·L-1的碱溶液调节混合溶液的pH值为5-8,25-100℃下反应12-36h,产物用去离子水离心洗涤,干燥,得到水杨酸根插层的一维双金属层状氢氧化锌钴前驱体;
2)将制得的水杨酸根插层的一维双金属层状氢氧化锌钴前驱体放置于广口瓶中,以5-100mL·min-1的流速向瓶内通入H2S气体反应1-30分钟,待反应完全后,于管式炉中300-400℃温度下惰性气体氛围中焙烧0.5-8h,得到一维Zn1-xCoxS固溶体与碳纳米复合光催化剂。
3.根据权利要求2所述的制备方法,其特征在于,步骤1)中所述的无机锌盐选自硝酸锌、氯化锌、硫酸锌中的一种或几种。
4.根据权利要求2所述的制备方法,其特征在于,步骤1)中所述的金属钴盐选自Co(NO3)2、CoCl2、CoSO4中的一种或几种。
5.根据权利要求2所述的制备方法,其特征在于,步骤1)中所述的水杨酸盐为水杨酸钠、水杨酸钾中的一种或两种。
6.根据权利要求2所述的制备方法,其特征在于,步骤1)中所述的碱溶液为NaOH、KOH、或尿素溶液。
7.根据权利要求2所述的制备方法,其特征在于,步骤2)中所述的惰性气体为氮气、氩气。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610311075.0A CN105964278B (zh) | 2016-05-11 | 2016-05-11 | 一种一维Zn1‑xCoxS固溶体与碳纳米复合光催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610311075.0A CN105964278B (zh) | 2016-05-11 | 2016-05-11 | 一种一维Zn1‑xCoxS固溶体与碳纳米复合光催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105964278A true CN105964278A (zh) | 2016-09-28 |
CN105964278B CN105964278B (zh) | 2018-02-13 |
Family
ID=56991610
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610311075.0A Active CN105964278B (zh) | 2016-05-11 | 2016-05-11 | 一种一维Zn1‑xCoxS固溶体与碳纳米复合光催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105964278B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108611658A (zh) * | 2018-05-03 | 2018-10-02 | 北京化工大学 | 一种一维多孔纳米复合材料及其制备方法和在电解水中的应用 |
CN109806888A (zh) * | 2019-02-23 | 2019-05-28 | 华南理工大学 | 1T-MoS2改性的ZnCoS固溶体空心十二面体纳米复合材料及其制备方法与应用 |
CN111266114A (zh) * | 2020-03-17 | 2020-06-12 | 北京化工大学 | 一种金属铁/氧化锌/碳三元纳米复合可见光催化剂及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10137598A (ja) * | 1996-11-15 | 1998-05-26 | Catalysts & Chem Ind Co Ltd | 水素化処理触媒の硫化方法およびそれを用いた炭化水素油の水素化処理方法 |
CN103159254A (zh) * | 2013-03-18 | 2013-06-19 | 新疆大学 | 一种固相制备硫化镉/氧化石墨复合材料的方法 |
-
2016
- 2016-05-11 CN CN201610311075.0A patent/CN105964278B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10137598A (ja) * | 1996-11-15 | 1998-05-26 | Catalysts & Chem Ind Co Ltd | 水素化処理触媒の硫化方法およびそれを用いた炭化水素油の水素化処理方法 |
CN103159254A (zh) * | 2013-03-18 | 2013-06-19 | 新疆大学 | 一种固相制备硫化镉/氧化石墨复合材料的方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108611658A (zh) * | 2018-05-03 | 2018-10-02 | 北京化工大学 | 一种一维多孔纳米复合材料及其制备方法和在电解水中的应用 |
CN109806888A (zh) * | 2019-02-23 | 2019-05-28 | 华南理工大学 | 1T-MoS2改性的ZnCoS固溶体空心十二面体纳米复合材料及其制备方法与应用 |
CN109806888B (zh) * | 2019-02-23 | 2021-03-30 | 华南理工大学 | 1T-MoS2改性的ZnCoS固溶体空心十二面体纳米复合材料及其制备方法与应用 |
CN111266114A (zh) * | 2020-03-17 | 2020-06-12 | 北京化工大学 | 一种金属铁/氧化锌/碳三元纳米复合可见光催化剂及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN105964278B (zh) | 2018-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Huang et al. | ZnxCd1-xS based materials for photocatalytic hydrogen evolution, pollutants degradation and carbon dioxide reduction | |
Yang et al. | One-step low-temperature synthesis of 0D CeO2 quantum dots/2D BiOX (X= Cl, Br) nanoplates heterojunctions for highly boosting photo-oxidation and reduction ability | |
Zhang et al. | Controllable growth of MoS2 nanosheets on novel Cu2S snowflakes with high photocatalytic activity | |
Yang et al. | SrTiO 3 nanocubes decorated with Ag/AgCl nanoparticles as photocatalysts with enhanced visible-light photocatalytic activity towards the degradation of dyes, phenol and bisphenol A | |
Liu et al. | Highly efficient and noble metal-free NiS modified MnxCd1-xS solid solutions with enhanced photocatalytic activity for hydrogen evolution under visible light irradiation | |
Yu et al. | Hydrothermal synthesis and characterization of novel PbWO4 microspheres with hierarchical nanostructures and enhanced photocatalytic performance in dye degradation | |
Bak et al. | Facile fabrication of pseudo-microspherical ZnO/CdS core-shell photocatalysts for solar hydrogen production by water splitting | |
Jiang et al. | Preparation of magnetically retrievable flower-like AgBr/BiOBr/NiFe2O4 direct Z-scheme heterojunction photocatalyst with enhanced visible-light photoactivity | |
CN101940933B (zh) | CdS量子点敏化Zn1-xCdxS光解水制氢可见光光催化剂制备方法 | |
Gong et al. | Controlled synthesis of bismuth-containing compounds (α-, β-and δ-Bi 2 O 3, Bi 5 O 7 NO 3 and Bi 6 O 6 (OH) 2 (NO 3) 4· 2H 2 O) and their photocatalytic performance | |
Qin et al. | Photocatalytic degradation of 2-Mercaptobenzothiazole by a novel Bi2WO6 nanocubes/In (OH) 3 photocatalyst: Synthesis process, degradation pathways, and an enhanced photocatalytic performance mechanism study | |
Li et al. | Halloysite–CeO2–AgBr nanocomposite for solar light photodegradation of methyl orange | |
Zhang et al. | Ag3VO4/BiOIO3 heterojunction with enhanced visible-light-driven catalytic activity | |
Xia et al. | Optimal rare-earth (La, Y and Sm) doping conditions and enhanced mechanism for photocatalytic application of ceria nanorods | |
Xing et al. | Facile one-pot synthesis and photocatalytic properties of hierarchically structural BiVO 4 with different morphologies | |
Liang et al. | One-step introduction of metallic Bi and non-metallic C in Bi 2 WO 6 with enhanced photocatalytic activity | |
Zhang et al. | Novel method of constructing CdS/ZnS heterojunction for high performance and stable photocatalytic activity | |
Motlagh et al. | Structural properties of nickel hydroxide/oxyhydroxide and oxide nanoparticles obtained by microwave-assisted oxidation technique | |
Mu et al. | Bimetallic metal–organic frameworks-derived mesoporous CdxZn1− xS polyhedrons for enhanced photocatalytic hydrogen evolution | |
Wang et al. | Mixed 1T-2H phase MoSe2 as interfacial charge-transfer-bridge to boosting photocatalytic activity of dual Z-scheme AgI/1T-2H MoSe2/Bi4O5Br2 heterojunction | |
CN105964278A (zh) | 一种一维Zn1-xCoxS固溶体与碳纳米复合光催化剂及其制备方法 | |
Otgonbayar et al. | Enhanced photocatalytic activity of CO 2 reduction to methanol through the use of a novel-structured CuCaAg 2 Se–graphene–TiO 2 ternary nanocomposite | |
Yu et al. | BixY1− xVO4 solid solution with porous surface synthesized by molten salt method for photocatalytic water splitting | |
Fang et al. | Construction and performance of a novel CuBi2O4/In2O3 Z-scheme heterojunction photocatalyst | |
Qi et al. | Partial Cu ion exchange induced triangle hexagonal Mn 0.45 Cu 0.05 Cd 0.5 S nanocrystals for enhanced photocatalytic hydrogen evolution |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |