CN105964278B - 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
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 239000006104 solid solution Substances 0.000 title claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229960001860 salicylate Drugs 0.000 claims abstract description 15
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 238000009830 intercalation Methods 0.000 claims abstract description 10
- 230000002687 intercalation Effects 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- CPOXHKWVHTWUGL-UHFFFAOYSA-J zinc;cobalt(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Zn+2] CPOXHKWVHTWUGL-UHFFFAOYSA-J 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion 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
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 241000219000 Populus Species 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 1
- 229960004889 salicylic acid Drugs 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007788 liquid Substances 0.000 description 10
- 238000009938 salting Methods 0.000 description 9
- 239000003643 water by type Substances 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
- 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
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- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- 240000000203 Salix gracilistyla Species 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
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- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229960004025 sodium salicylate Drugs 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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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 (6)
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，固溶体粒子尺寸为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5-100 mL·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2）中所述的惰性气体氛围为氮气、氩气。
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