CN108855222A - ZCS@Ni-MOF纳米复合材料及其制备和应用 - Google Patents
ZCS@Ni-MOF纳米复合材料及其制备和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019441 ethanol Nutrition 0.000 claims abstract description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 13
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- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000006303 photolysis reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 8
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- 239000011701 zinc Substances 0.000 description 105
- 229960004756 ethanol Drugs 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- -1 example Such as Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- 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
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- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- 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
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
本发明提供了一种Ni‑MOF包覆ZCS的纳米复合材料Zn0.5Cd0.5S@Ni‑MOF（x%）的制备方法，是先以乙醇为溶剂，采用溶剂热法合成了Zn0.5Cd0.5S；再将Ni(NO3)2·6H2O、聚乙烯吡咯烷酮、Zn0.5Cd0.5S溶于乙醇中，超声、搅拌后于80℃~90℃保持4~8小时，离心分离，产物用乙醇洗涤，干燥，即得目标产物ZCS@Ni‑MOF。光催化性能测试结果表明，在可见光照射下，ZCS@Ni‑MOF的产氢速率最高可达2800μmol/h/0.1g，是纯ZCS的5.6倍。
Description
技术领域
本发明涉及一种Ni-MOF纳米复合材料的制备，尤其涉及一种Ni-MOF包覆ZCS的纳米复合材料的制备，只要作为光催化剂用于光解水产氢反应中。
背景技术
近年来，由于工业生产过度使用化石燃料，导致能源短缺和环境污染。氢气作为可再生的清洁燃料是取代传统化石燃料最有前景的能源载体之一。由于太阳能的巨大潜力，太阳能光解生产氢是生产氢能最直接、最有效的手段。自20世纪70年代以来，本田和藤岛已经使用二氧化钛将水光催化转化为H2和O2，越来越多的研究人员开始探索如何通过光催化将水转化为氢。在制备良好和应用的光催化剂中，ZnxCd1-xS基材料等金属硫化物由于其可调带隙和低成本而被认为是有前途的候选材料。例如，Zn0.5Cd0.5S的带隙可以通过材质中Zn和Cd的添加比例调整。根据之前的报道，Zn0.5Cd0.5S在可见光照射下的水分解过程中表现出一定的性能，在反应前后保持一致的化学稳定性。然而，Zn0.5Cd0.5S的应用由于其强烈的电子空穴复合仍然受到限制。为了减少载流子的光诱导复合，贵金属通常被用作助催化剂，例如，Pt是最活泼的放氢助催化剂，但其成本高，稀释性差，成为其实际应用的障碍。因此，发掘低成本的非贵金属助催化剂已经成为一个挑战。
近年来，结晶性多孔材料（MOFs）由于其比表面积大，孔径大小易于控制，易于改性等优点，在各个领域引起了广泛的研究。例如，MOFs已成功地与一系列活性物质（包括金属纳米粒子，金属氧化物和有机聚合物）结合在一起，不仅展现了他们构建的MOFs和NPs的固有性质，而且还具有其在新领域的协同性能。它们被用于水分子捕获，工业分离，气体储存，光催化等领域。然而，在核壳NPs@MOFs纳米结构中使用光催化剂作为核的报道很少。
发明内容
本发明的目的是提供了Zn0.5Cd0.5S@Ni-MOF复合材料的制备方法；
本发明的另一目的，是对制备的Zn0.5Cd0.5S@Ni-MOF复合材料的结构及在光解水产氢的应用性能进行研究。
一、ZCS@Ni-MOF复合材料的制备
（1）Zn0.5Cd0.5S的合成
以乙醇为溶剂，采用溶剂热法合成了Zn0.5Cd0.5S。具体合成工艺为：将Zn(NO3)2·6H2O和Cd(NO3)2·4H2O溶于乙醇中形成混合液；再向混合液中加入(NH4)2S，并搅拌15~25分钟，然后加热至180~220℃下反应22~26小时；产物用蒸馏水和乙醇交替洗涤，干燥，即得Zn0.5Cd0.5S，标记为ZCS。
Zn(NO3)2·6H2O和Cd(NO3)2·4H2O的摩尔比控制在1:1.5~1:0.5；
(NH4)2S的加入量为Zn(NO3)2·6H2O和Cd(NO3)2·4H2O总摩尔量的4~6倍。
（2）Zn0.5Cd0.5S@Ni-MOF(x%)核壳纳米材料的合成
将Ni(NO3)2·6H2O、聚乙烯吡咯烷酮（PVP，可提供配位基团使其与Ni2+形成配位化合物）、Zn0.5Cd0.5S溶于乙醇中，超声处理5~15min，再搅拌15~25min，然后于80~90℃保持4~8小时，离心分离，产物用乙醇洗涤，干燥，即得目标产物Zn0.5Cd0.5S@Ni-MOF，标记为ZCS@Ni-MOF。
Ni(NO3)2·6H2O与聚乙烯吡咯烷酮(PVP)的质量比为1:2~1:3；Ni(NO3)2·6H2O与Zn0.5Cd0.5S的摩尔比为1:0.5~1:0.3。
所制备的ZCS@Ni-MOF(x%)中，Ni-MOF的质量百分数为5~20％。
二、Ni-MOF包覆ZCS复合材料的表征
1、XRD图
图1为ZCS和ZCS@Ni-MOF（5~20％）的XRD图。从图1a中可以看出，样品在27.4、31.6、45.75、54.1处的所有111，200，220，311面均代表所有样品Zn0.5Cd0.5S@NiMOF的衍射峰与纯Zn0.5Cd0.5S相比几乎没有偏移。图1b显示了光催化产氢反应前后Zn0.5Cd0.5S@Ni-MOF(15%)的XRD衍射峰。可以清楚地看到，反应前后Zn0.5Cd0.5S@Ni-MOF(15%)的XRD衍射峰几乎没有变化，表明Zn0.5Cd0.5S@Ni-MOF(15%)非常稳定。
2、SEM图
图2 （a、b）为Ni-MOF和（c、d）Zn0.5Cd0.5S的扫描电镜谱图。从图中可以合成的Ni-MOF是均匀的八面体，分散性较好，Zn0.5Cd0.5S样品是大小为50~100nm左右的纳米颗粒，而且分散比较均匀。图（e、f）是包裹了Ni-MOF之后的Zn0.5Cd0.5S@Ni-MOF(15%)的透射电镜图。从图中可以明显看出核壳结构，而且样品整体的纳米尺寸变大，外层为Ni-MOF，内层为Zn0.5Cd0.5S纳米颗粒，并且包覆了Ni-MOF后，样品有所团聚。
3、XPS谱
为了进一步评估Zn0.5Cd0.5S@Ni-MOF(15%)中元素的存在状态，对样品做了XPS分析。图3显示了Zn 2p31/2，Zn 2p33/2（a），Cd 3d3/2，Cd 3d5/2（b），S 2p3/2，S 2p1/2（c）和Ni 2p1/2，Ni2p3/2（d）的XPS谱图。以284.6eV的C 1s峰作为参考结合分析。从图3（a、b）可以看出，在1022.6和1045.6 eV处的结合能分别与Zn 2p3/2和2p1/2的结合能一致。在405.3和412.1 eV处的结合能分别为Cd 3d5/2和Cd 3d3/2的结合能相对应。并且这四个峰形比较是尖锐，表明Zn和Cd的化合价都是+2。图3c是S 2p的XPS谱图，根据前面分析可知Zn0.5Cd0.5S@Ni-MOF（15％）的S2p峰可以拟合为结合能分别在161.7和162.8eV处的S 2p3/2和S 2p1/2峰。图3d显示的是在结合能852.8和871.9eV处是Ni 2p拟合出的Ni 2p3/2和2p1/2峰，根据对照结合能标准表可以发现Ni-MOF中的Ni为+2价。当Zn0.5Cd0.5S@Ni-MOF（15％）中的电子处于激发中间态时，它们将减弱H+还原成H2的能力，研究人员发现Ni具有相对较小的氢吸附热（约109~134kJ / mol，Pt为109 kJ / mol）。此外，根据交换电流与氢生成过程中MH的结合强度（M代表过渡金属）之间的关系，Ni的活化能在所有非贵金属中最低，甚至可以起到在产氢过程中的作用相当于Pt。这些概念解释了质子Ni或其氧化物与Pt相比在还原过程中可能发挥的作用：它们通过促进氢气吸附 - 还原 - 解吸过程来促进传质过程。
4、紫外-可见吸收光谱
图4a是Zn0.5Cd0.5S和Zn0.5Cd0.5S@Ni-MOF(x%)样品的UV-vis DRS光谱图。 从UV-vis DRS谱图中可以看出Zn0.5Cd0.5S纳米粒子的吸收边在520nm处。与Zn0.5Cd0.5S纳米粒子相比，光催化剂Zn0.5Cd0.5S@Ni-MOF（15%）具有更强的吸收强度，并且吸收边红移至560nm，表明在Zn0.5Cd0.5S光催化剂中引入的Ni-MOF具有明显的带隙变化。图4显示了不同比例Zn0.5Cd0.5S@Ni-MOF(x%)样品的UV-vis DRS光谱，从图中可以看出Zn0.5Cd0.5S@Ni-MOF(x%)的紫外可见漫反射光谱随着包裹Ni-MOF少到多，Zn0.5Cd0.5S@Ni-MOF的吸收强度依次增大。图4b是激发波长为380nm时Zn0.5Cd0.5S和Zn0.5Cd0.5S@Ni-MOF(x%)的光致发光光谱图。从图中可以看出Zn0.5Cd0.5S和Zn0.5Cd0.5S@Ni-MOF的光致发光峰位于472nm，这可归因于锌空位，ZnS相关发光性能以及光生电子和空穴的复合所引起的,并且可以看出Zn0.5Cd0.5S@Ni-MOF(15％)的荧光峰强度明显弱于其他包覆Ni-MOF量的Zn0.5Cd0.5S@Ni-MOF(x％)，表明Zn0.5Cd0.5S@Ni-MOF(15％)纳米复合材料中光生电子和空穴的复合几率更低，更有利于光催化过程中光生电子的传输，也就是说Zn0.5Cd0.5S@Ni-MOF(15％)具有最好的光催化产氢活性。
三、ZCS@Ni-MOF(x%)复合材料的光催化性能
1、光电化学性能
采用三电极系统（CHI-660DCo.，Shanghai，China）在LED灯（λ>420nm，CEL-LED100）照明条件下获得光电极的光电化学（PEC）性能。
图5 (a) 图是Zn0.5Cd0.5S和Zn0.5Cd0.5S@Ni-MOF(x%)的光电流曲线图，图5（b）是Zn0.5Cd0.5S和Zn0.5Cd0.5S@Ni-MOF(x%)的奈奎斯特曲线图。从图5 (b)中可以看出，与Zn0.5Cd0.5S纳米粒子相比，光催化剂Zn0.5Cd0.5S@Ni-MOF（x％）的半圆半径随着Ni-MOF包覆量的曾加变得越来越小，表明随着Ni-MOF量的增加Zn0.5Cd0.5S@Ni-MOF（x％）的阻抗越来越小，当包覆Ni-MOF的量达到15%时曲线具有最小的半圆半径，说明Zn0.5Cd0.5S@Ni-MOF(15％)的阻抗最小。图5 (a)是Zn0.5Cd0.5S和Zn0.5Cd0.5S@Ni-MOF(x％)的瞬态光电流曲线图，从图中可以看出随着Ni-MOF包覆量的增加Zn0.5Cd0.5S@Ni-MOF(x％)的瞬态光电流越来越大，当Ni-MOF包覆量达到15%时，Zn0.5Cd0.5S@Ni-MOF(15％)的光电流强度约是纯Zn0.5Cd0.5S光电流的8倍，表明Zn0.5Cd0.5S@Ni-MOF(15％)在硫酸钠缓冲溶液中具有比Zn0.5Cd0.5S更低的界面电荷转移电阻。即Zn0.5Cd0.5S@Ni-MOF(15％)表面上的界面电荷转移比在Zn0.5Cd0.5S表面界面上的电荷转移要快。采用牺牲剂硫化钠和亚硫酸钠捕获Zn0.5Cd0.5S和Zn0.5Cd0.5S@Ni-MOF(15％)表面上产生的光致空穴，一定程度上减小避免光生电子和空穴的复合效率。从图5中可以得出Zn0.5Cd0.5S@Ni-MOF(15％)比Zn0.5Cd0.5S具有更好的光催化产氢活性。
2、光催化性能测试
Zn0.5Cd0.5S@Ni-MOF(x%)的光催化活性在反应器中进行。在每个试验中，将0.1g光催化剂粉末分散在100 ml0.5M Na2S·9H2O和0.5M Na2SO3的水溶液中。然后使用与420nm截止滤器（0.1MNaNO2水溶液）组合的300WXe灯在可见光照射下混合物。在测试周期期间，使用气相色谱（GC-9560，中国）每小时一次分离放出的H2。H2的量通过热导检测器（Ar载体）测量。
在LED灯（λ>420nm，CELLED100）照明的条件下，采用三电极系统获得光电阳极的光电化学（PEC）性能。铂丝和Ag/AgCl分别用作反电极和参比电极。工作电极在氟化锡氧化物（FTO）的导体玻璃上制成。将样品（10mg）均匀分散于无水乙醇中并超声20分钟，然后将其缓慢滴加到FTO玻璃上。工作电极在红外灯照射下干燥30分钟。电解质是在石英器皿中的0.5MNa2SO4（pH=7.5）水溶液。用0.5V的偏压电压进行光电化学测试。使用通过FTO背面的照明，照明面积约为1.0cm2。
图6（a）为可见光照射下，在100 ml 0.5 M Na2S和0.5 M Na2SO3水溶液中ZCS和Zn0.5Cd0.5S@Ni-MOF（5~20％）的光催化H2析出速率（加入光催化剂：0.1g）；利用封闭气体循环系统对水解产生的光催化氢气进行了测试，在可见光照射下，使用0.5 M Na2S和0.5 MNa2SO3作为保护剂。图6a显示了在可见光照射下，Zn0.5Cd0.5S@Ni-MOF（5~20％）比纯ZCS具有更高的产氢性能。当Ni-MOF量达到15％时，产氢速率可达2800μmol/h/0.1g，是纯ZCS的5.6倍。
稳定性是催化剂的一个非常重要的因素，图6b显示了在相同条件下进行的H2析出的Zn0.5Cd0.5S@Ni-MOF（15％）的循环稳定性实验。通过循环稳定性实验可以发现，经过四个循环后，Zn0.5Cd0.5S@Ni-MOF（15％）的析氢速率几乎没有下降。也就是说，经过长时间的光催化反应后，Zn0.5Cd0.5S@Ni-MOF（15％）的化学性质没有变化。说明Zn2p和Cd3d的结合能在反应前没有变化，Zn0.5Cd0.5S@Ni-MOF（15％）在保持高性能的同时具有良好的循环稳定性。值得注意的是，S2-也表现出良好的稳定性，这是因为溶液中的牺牲剂S2-和SO3 2-能够抑制Zn0.5Cd0.5S@Ni-MOF（15％）中的S2-氧化。
综上所述，我们合成了Zn0.5Cd0.5S@Ni-MOF，可以提高可见光照射下的光催化活性。ZCS中掺杂的Ni可以捕获光诱导电子，然后在反应过程中将H+还原成H2，S2-与ZCS在Na2SO3/Na2S溶液中捕获光致空穴。因此，光致电子和光致空穴被分开。光诱导电子可以与O2结合形成O2-，孔和O2-可以用来催化苯甲醇形成苯甲醛。接下来，电子和空穴迁移到催化剂表面上的活性位点。催化剂表面的电子可以减少H+在水中产生氢气，而O2 -和空穴将醇氧化成相应的醛。在这个过程中，光诱导电荷载体的分离是关键的一步，因为光诱导电子和空穴往往会迅速重组，这反过来将加剧不利的光催化活性的氢气演变和催化氧化。
附图说明
图1为ZCS和Zn0.5Cd0.5S@Ni-MOF(x%)的XRD图。
图2为Ni-MOF(a,b)，Zn0.5Cd0.5S(c,d) 的扫描电镜图，（e,f）为Zn0.5Cd0.5S @Ni-MOF(15%)的透射电镜谱图。
图3为Zn，Cd，S和Ni的高分辨率XPS谱。
图4为ZCS和Zn0.5Cd0.5S@Ni-MOF(x%)的紫外-可见吸收光谱（a）及在380nm激发的合成Cd0.5Zn0.5S的光致发光光谱（b）。
图5为ZCS和Zn0.5Cd0.5S@Ni-MO(x%)F电极的EIS奈奎斯特曲线（a）电极在0.5M硫酸钠缓冲溶液中可见光照射下的光电流曲线（b）。
图6为ZCS和Zn0.5Cd0.5S@Ni-MOF(x%)的光催化H2析出速率（a）及Zn0.5Cd0.5S@Ni-MOF（15％）的产氢循环稳定性（b）。
具体实施方式
实施例1
（1）Zn0.5Cd0.5S的合成：将2.5mmol Zn(NO3)2·6H2O和2.5mmol Cd(NO3)2·4H2O溶于20ml乙醇中；再将7.5mmol(NH4)2S滴入上述混合溶液中并搅拌20分钟，然后将其转移到Teflon衬里中（内衬用不锈钢高压釜密封）并向其中加入50ml乙醇，在200℃保持24小时。反应结束后后，交替使用蒸馏水和乙醇清洁洗涤，产物在80℃的烘箱中干燥，即得Zn0.5Cd0.5S；
（2）Zn0.5Cd0.5S@Ni-MOF(15%)核壳纳米结构的合成：将4.5 mmol Ni(NO3)2·6H2O、3gPVP、0.3g Zn0.5Cd0.5S溶于200ml C2H6O中，将混合溶液先超声处理15 min，再搅拌20 min，使用回流装置在85℃反应6小时；离心分离，产物用乙醇洗涤10次，80 ℃下干燥，即得Zn0.5Cd0.5S@Ni-MOF（15%）。
ZCS@Ni-MOF（15%）用于光解水产氢反应中，产氢速率可达2800μmol/h/0.1g。
实施例2
（1）Zn0.5Cd0.5S的合成：同实施例1；
（2）Zn0.5Cd0.5S@Ni-MOF(5%)的合成：将1.5 mmol Ni(NO3)2·6H2O、1g PVP、0.3 gZn0.5Cd0.5S溶于200ml C2H6O中，将混合溶液先超声处理15 min，再搅拌20 min，使用回流装置在85℃反应6小时，离心分离，产物用乙醇洗涤10次，80℃下干燥，即得Zn0.5Cd0.5S@Ni-MOF。该品种中Ni-MOF的含量为5%，记为ZCS@Ni-MOF（5%）。
ZCS@Ni-MOF（5%）用于光解水产氢反应中，产氢速率可达1100 μmol/h/0.1g。
实施例3
（1）Zn0.5Cd0.5S的合成：同实施例1；
（2）Zn0.5Cd0.5S@Ni-MOF(10%)的合成：将3.0 mmol Ni(NO3)2·6H2O、2g PVP、0.3gZn0.5Cd0.5S溶于200ml C2H6O中，将混合溶液先超声处理15min，再搅拌20min，使用回流装置在85℃反应6小时，离心分离，产物用乙醇洗涤10次，80℃下干燥，即得Zn0.5Cd0.5S@Ni-MOF。该品种中Ni-MOF的含量为10%，记为ZCS@Ni-MOF（10%）。
ZCS@Ni-MOF（10%）用于光解水产氢反应中，产氢速率可达1500 μmol/h/0.1g。
实施例4
（1）Zn0.5Cd0.5S的合成：同实施例1；
（2）Zn0.5Cd0.5S@Ni-MOF(20%)的合成：将6.0mmol Ni(NO3)2·6H2O、4g PVP、0.3gZn0.5Cd0.5S溶于200ml C2H6O中，将混合溶液先超声处理15min，再搅拌20min，使用回流装置在85℃反应6小时，离心分离，产物用乙醇洗涤10次，80℃下干燥，即得Zn0.5Cd0.5S@Ni-MOF。该品种中Ni-MOF的含量为20%，记为ZCS@Ni-MOF（20%）。
ZCS@Ni-MOF（20%）用于光解水产氢反应中，产氢速率可达2200 μmol/h/0.1g。
Claims (6)
1.ZCS@Ni-MOF纳米复合材料的制备方法，包括以下步骤：
（1）Zn0.5Cd0.5S的合成：将Zn(NO3)2·6H2O和Cd(NO3)2·4H2O溶于乙醇中形成混合液；再向混合液中加入(NH4)2S，并搅拌20~30分钟，然后加热至180℃~220℃下反应22~26小时；产物用蒸馏水和乙醇交替洗涤，干燥，即得Zn0.5Cd0.5S，标记为ZCS；
（2）ZCS@Ni-MOF纳米复合材料的合成：将Ni(NO3)2·6H2O、聚乙烯吡咯烷酮、Zn0.5Cd0.5S溶于乙醇中，超声处理5~15min，再搅拌15~25min，然后于80℃~90℃保持4~8小时，离心分离，产物用乙醇洗涤，干燥，即得目标产物ZCS@Ni-MOF。
2.如权利要求1所述ZCS@Ni-MOF米复合材料的制备方法，其特征在：步骤（1）中，Zn(NO3)2·6H2O和Cd(NO3)2·4H2O的摩尔比控制在1:1.5~1:0.5。
3.如权利要求1所述ZCS@Ni-MOF纳米复合材料的制备方法，其特征在：步骤（1）中，(NH4)2S的加入量为Zn(NO3)2·6H2O和Cd(NO3)2·4H2O总摩尔量的4~6倍。
4.如权利要求1所述ZCS@Ni-MOF纳米复合材料的制备方法，其特征在：步骤（2）中，Ni(NO3)2·6H2O与聚乙烯吡咯烷酮的质量比为1:2~1:3。
5.如权利要求1所述ZCS@Ni-MOF纳米复合材料的制备方法，其特征在：步骤（2）中，Ni(NO3)2·6H2O与Zn0.5Cd0.5S的摩尔比为1:0.5~1:0.3。
6.如权利要求1所述方法制备的ZCS@Ni-MOF纳米复合材料作为光催化剂用于光解水产氢反应中。
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