CN102302941A - A kind of photocatalyst supporting Pt-Pd-Cr2O3 composite co-catalyst and its preparation method and application - Google Patents
A kind of photocatalyst supporting Pt-Pd-Cr2O3 composite co-catalyst and its preparation method and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003426 co-catalyst Substances 0.000 title abstract description 30
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 239000000084 colloidal system Substances 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 53
- 230000001699 photocatalysis Effects 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 22
- -1 platinum ion Chemical class 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 15
- 229910001430 chromium ion Inorganic materials 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 9
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 229910018879 Pt—Pd Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910001092 metal group alloy Inorganic materials 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 8
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开了一种负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂及其制备方法和应用。所述的一种负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂，即Pt及Pd形成的合金负载于CdS催化剂表面，Cr2O3负载于Pd-Pt/CdS表面形成Cr2O3薄层。其制备方法即包括金属合金纳米胶体的制备、以及CdS光催化剂的改性等2个步骤，最终得一种负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂。本发明的Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂可大幅提高CdS光催化剂分解水制氢活性，另外本发明的制备方法简单易行、不需要复杂昂贵的设备、合成条件温和，有利于大规模推广。
The invention discloses a CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite co-catalyst, its preparation method and application. The CdS photocatalyst supporting Pt-Pd-Cr 2 O 3 composite co-catalyst, that is, the alloy formed by Pt and Pd is loaded on the surface of the CdS catalyst, and Cr 2 O 3 is loaded on the surface of Pd-Pt/CdS to form Cr 2 O 3 TLC. The preparation method includes two steps: the preparation of metal alloy nano-colloid and the modification of CdS photocatalyst, and finally a CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite co-catalyst is obtained. The CdS photocatalyst of the Pt-Pd-Cr 2 O 3 composite co-catalyst of the present invention can greatly improve the hydrogen production activity of the CdS photocatalyst by splitting water. In addition, the preparation method of the present invention is simple and easy, does not require complex and expensive equipment, and has mild synthesis conditions , which is conducive to large-scale promotion.
Description
技术领域 technical field
本发明属于新能源开发技术领域中的光催化技术，特别涉及一种负载 The invention belongs to photocatalytic technology in the technical field of new energy development, in particular to a load
Pt-Pd-Cr2O3复合助催化剂的光催化剂及其制备方法和应用。 Photocatalyst of Pt-Pd-Cr 2 O 3 composite co-catalyst and its preparation method and application.
背景技术 Background technique
光催化分解水生成氢气的过程可看作是发生于半导体催化剂表面的一个催化还原反应。研究中人们发现在催化剂表面镀上一些贵金属或金属氧化物（如Pt, Pd, Au, Rh，Ru和NiO）可大幅提高光催化剂的光催化活性，这类贵金属和金属氧化物被称为光催化助催化剂(cocatalyst)。然而相对于新型光催化剂的研制探索而言，新型光催化助催化剂的研究尚未得到广泛重视，这方面的研究也少有报道。 The process of photocatalytic water splitting to generate hydrogen can be regarded as a catalytic reduction reaction on the surface of semiconductor catalysts. In the research, it was found that coating some noble metals or metal oxides (such as Pt, Pd, Au, Rh, Ru and NiO) on the surface of the catalyst can greatly improve the photocatalytic activity of the photocatalyst. Such noble metals and metal oxides are called photocatalysts. Catalytic cocatalyst. However, compared with the development and exploration of new photocatalysts, the research on new photocatalytic co-catalysts has not received widespread attention, and there are few reports in this area.
负载光催化助催化剂（如Pt和Rh等）是提高光催化剂活性的一种重要技术手段。然而常规光催化助催化剂的负载方法，光还原沉积法和热分解沉积法，需要对催化剂进行预处理，使用时比较复杂，其中热分解沉积技术还需要进行300～600℃的高温处理，这会严重限制含硫和含氮等具备高活性但高温下不太稳定的光催化剂的使用。 Supporting photocatalytic co-catalysts (such as Pt and Rh, etc.) is an important technical means to improve the activity of photocatalysts. However, the conventional photocatalytic co-catalyst loading methods, photoreduction deposition method and thermal decomposition deposition method, require pretreatment of the catalyst, which is more complicated to use. Among them, thermal decomposition deposition technology also requires high temperature treatment at 300-600 ° C, which will Severely restrict the use of sulfur- and nitrogen-containing photocatalysts that have high activity but are not stable at high temperatures.
本发明利用化学还原方法成功制备出一种以贵金属钯、铂和氧化铬复合负载为代表的氧化铬复合光催化助催化剂。实验结果表明，利用化学还原方法制备氧化铬基复合光催化助催化剂简洁有效，并且勿需对光催化剂进行预处理就可大幅提高催化剂的光催化活性。 The invention successfully prepares a chromium oxide composite photocatalytic co-catalyst represented by the composite loading of precious metal palladium, platinum and chromium oxide by using a chemical reduction method. The experimental results show that the preparation of chromium oxide-based composite photocatalytic co-catalyst by chemical reduction method is simple and effective, and the photocatalytic activity of the catalyst can be greatly improved without pretreatment of the photocatalyst.
发明内容 Contents of the invention
本发明的目的之一是为了解决现有技术中CdS催化剂光催化分解水制氢活性较低的问题，而提供一种负载复合光催化助催化剂Pt-Pd-Cr2O3的CdS光催化剂。 One of the purposes of the present invention is to provide a CdS photocatalyst loaded with a composite photocatalytic co-catalyst Pt-Pd-Cr 2 O 3 in order to solve the problem of low photocatalytic hydrogen production activity of CdS catalysts in the prior art.
本发明的目的之二在于提供一种上述的一种负载复合光催化助催化剂Pt-Pd-Cr2O3的CdS光催化剂的制备方法。即通过对光催化剂CdS进行表面改性，并且制备方法简单易行、不需要复杂昂贵的设备、合成条件温和。 The second object of the present invention is to provide a method for preparing the above-mentioned CdS photocatalyst loaded with composite photocatalytic co-catalyst Pt-Pd-Cr 2 O 3 . That is, the surface modification of the photocatalyst CdS is carried out, and the preparation method is simple, does not require complex and expensive equipment, and the synthesis conditions are mild.
本发明的目的之三在于上述的负载复合光催化助催化剂Pt-Pd-Cr2O3的CdS光催化剂在光催化分解水制氢方面的应用方法。 The third object of the present invention is the application method of the above-mentioned CdS photocatalyst loaded with composite photocatalytic co-catalyst Pt-Pd-Cr 2 O 3 in the aspect of hydrogen production by photocatalytic decomposition of water.
本发明的技术方案 Technical scheme of the present invention
一种负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂，Pt-Pd合金负载于CdS光催化剂表面，Cr2O3负载于Pt-Pd/CdS光催化剂表面形成Cr2O3薄层； A CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite promoter, Pt-Pd alloy loaded on the surface of CdS photocatalyst, Cr 2 O 3 loaded on the surface of Pt-Pd/CdS photocatalyst to form Cr 2 O 3 thin film layer;
其中Pt-Pd合金的粒径大小为1～10nm，Cr2O3薄层的厚度为4～5nm； The particle size of the Pt-Pd alloy is 1-10nm, and the thickness of the Cr 2 O 3 thin layer is 4-5nm;
其中Pt、Pd、Cr2O3 及CdS光催化剂的质量比即Pt：Pd：Cr2O3 ：CdS光催化剂为0～0.4：0～0.5：0～0.5：100。 The mass ratio of Pt, Pd, Cr 2 O 3 and CdS photocatalyst, that is, Pt:Pd:Cr 2 O 3 :CdS photocatalyst, is 0-0.4:0-0.5:0-0.5:100.
上述的一种负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂的制备方法，包括如下制备步骤： A kind of above-mentioned preparation method of the CdS photocatalyst of supporting Pt-Pd-Cr 2 O 3 composite promoters, comprises following preparation steps:
（1）、金属纳米胶体的制备 (1) Preparation of metal nanocolloids
取氯化钯水溶液，氯铂酸水溶液以及硝酸铬水溶液于容器中，均匀搅拌后得到钯离子、铂离子和铬离子的混合溶液1； Take an aqueous palladium chloride solution, an aqueous solution of chloroplatinic acid and an aqueous solution of chromium nitrate in a container, and stir evenly to obtain a mixed solution 1 of palladium ions, platinum ions and chromium ions;
其中Pt离子、Pd离子和Cr离子的质量比，即Pt离子：Pd离子：Cr离子为0～0.4：0～0.5：0～0.5； Among them, the mass ratio of Pt ions, Pd ions and Cr ions, that is, Pt ions: Pd ions: Cr ions is 0-0.4: 0-0.5: 0-0.5;
在不间断搅拌状态下，将PVP（聚乙烯基吡咯烷酮）溶液滴加入上述制备的钯离子、铂离子和铬离子的混合溶液1中，得钯离子、铂离子和铬离子的混合溶液2；其中PVP溶液的滴加量按与混合溶液1的体积比即PVP溶液：混合溶液1为0.1～1：10； Under continuous stirring, the PVP (polyvinylpyrrolidone) solution is added dropwise to the mixed solution 1 of palladium ions, platinum ions and chromium ions prepared above to obtain a mixed solution 2 of palladium ions, platinum ions and chromium ions; The amount of PVP solution to be added is based on the volume ratio of the mixed solution 1, that is, the PVP solution: the mixed solution 1 is 0.1 to 1:10;
随后配置的0.1～0.2mol/L NaBH4水溶液，按体积比即NaBH4水溶液：Pt离子、Pd离子和Cr离子的混合溶液2为1～10ml :100ml将NaBH4水溶液滴加入Pt离子、Pd离子和Cr离子的混合溶液2中，继续搅拌30min得到金属纳米胶体； The 0.1～0.2mol/L NaBH aqueous solution that configures subsequently, by volume ratio is NaBH aqueous solution : the mixed solution 2 of Pt ion, Pd ion and Cr ion is 1～10ml: 100ml adds NaBH aqueous solution dropwise to Pt ion, Pd ion In the mixed solution 2 of Cr ion, continue stirring for 30min to obtain metal nano colloid;
（2）、CdS光催化剂的改性 (2), Modification of CdS photocatalyst
取CdS光催化剂，加入步骤（1）制备的金属纳米胶体中，并进行超声吸附10～30min，其加入比例按CdS光催化剂与金属纳米胶体的质量比即CdS光催化剂：金属纳米胶体为1000：0～10，再加入氨水调节溶液pH至7～9，将悬浊液过滤、洗涤、60℃烘干、研磨20～30min，即得到本发明的一种负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂。 Take the CdS photocatalyst, add it to the metal nanocolloid prepared in step (1), and carry out ultrasonic adsorption for 10 to 30 minutes, and the addition ratio is based on the mass ratio of the CdS photocatalyst to the metal nanocolloid, that is, CdS photocatalyst:metal nanocolloid is 1000: 0 to 10, then add ammonia water to adjust the pH of the solution to 7 to 9, filter the suspension, wash, dry at 60°C, and grind for 20 to 30 minutes to obtain a loaded Pt-Pd-Cr 2 O 3 composite Cocatalyst CdS photocatalyst.
上述所得的一种负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂可用于光催化分解水制氢的反应。 The above-obtained CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite co-catalyst can be used for photocatalytic decomposition of water to produce hydrogen.
本发明的有益效果 Beneficial effects of the present invention
本发明的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂，相对于传统的CdS光催化剂而言，由于有助催化剂Pt-Pd-Cr2O3负载，使得其在促使光生电子和光生空穴分离，以及增大催化剂对溶液中的游离的氢离子和氢氧根的吸附性等方面的性能有所提高，将其应用于光催化分解水制氢中，可以大幅提高CdS分解水制氢活性。当Pt的添加量为CdS光催化剂质量的0.3wt.%时，有助催化剂Pt-Pd-Cr2O3负载的CdS光催化剂光催化分解水制氢活性最高，此时制氢光量子效率可达50.5%（420nm可见光照射时）。 Compared with the traditional CdS photocatalyst, the CdS photocatalyst supporting Pt-Pd-Cr 2 O 3 composite co-catalyst of the present invention, because of the co-catalyst Pt-Pd-Cr 2 O 3 loading, makes it promote photogenerated electrons Separation from photogenerated holes, as well as increasing the performance of the catalyst in the adsorption of free hydrogen ions and hydroxide ions in the solution have been improved, and it can be applied to photocatalytic water splitting to produce hydrogen, which can greatly improve the decomposition of CdS Hydrogen production activity of water. When the amount of Pt added is 0.3wt.% of the mass of the CdS photocatalyst, the CdS photocatalyst supported by the co-catalyst Pt-Pd-Cr 2 O 3 has the highest photocatalytic hydrogen production activity, and the photoquantum efficiency of hydrogen production can reach 50.5% (when irradiated with 420nm visible light).
另外本发明的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂的制备方法简单易行、不需要复杂昂贵的设备、合成条件温和，有利于大规模的推广。 In addition, the preparation method of the CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite co-catalyst of the present invention is simple and easy, does not require complex and expensive equipment, and has mild synthesis conditions, which is conducive to large-scale promotion.
附图说明 Description of drawings
图1、Pt-Pd-Cr2O3复合助催化剂的负载对CdS光催化分解水制氢活性的影响 Figure 1. Effect of Pt-Pd-Cr 2 O 3 composite co-catalyst loading on CdS photocatalytic water splitting hydrogen production activity
图2、不同助催化剂的负载对CdS光催化分解水制氢活性的影响 Figure 2. Effect of loading of different cocatalysts on CdS photocatalytic water splitting hydrogen production activity
图3、Pt负载量对Pt-Pd-Cr2O3/CdS光催化剂分解水制氢产量的影响 Figure 3. The effect of Pt loading on the production of hydrogen from water splitting by Pt-Pd-Cr 2 O 3 /CdS photocatalyst
图4、Pt负载量对Pt-Pd-Cr2O3/CdS光催化剂分解水制氢速率的影响。 Figure 4. The effect of Pt loading on the rate of hydrogen production from water splitting by Pt-Pd-Cr 2 O 3 /CdS photocatalyst.
具体实施方式 Detailed ways
下面通过实施例并结合附图对本发明进一步阐述，但并不限制本发明。 The present invention will be further elaborated below by means of embodiments in conjunction with the accompanying drawings, but the present invention is not limited.
实施例1Example 1
负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂的制备方法，步骤如下： The preparation method of the CdS photocatalyst of load Pt-Pd-Cr 2 O 3 composite promoters, the steps are as follows:
称取浓度为1g/L的氯化钯水溶液2ml、浓度为0.5g/L的氯铂酸水溶液3ml，以及浓度为0.5g/L的硝酸铬水溶液0.5ml于10ml烧杯中，搅拌10min，得到钯离子、铂离子和铬离子的混合溶液1; Take by weighing the palladium chloride aqueous solution 2ml that concentration is 1g/L, the chloroplatinic acid aqueous solution 3ml that concentration is 0.5g/L, and the chromium nitrate aqueous solution 0.5ml that concentration is 0.5g/L in the 10ml beaker, stir 10min, obtain palladium A mixed solution of ions, platinum ions and chromium ions 1;
在不间断搅拌状态下，将浓度为10 g/L的PVP溶液0.5ml滴加入上述制备的钯离子和铬离子的混合溶液1中，得到钯离子、铂离子和铬离子的混合溶液2； Under uninterrupted stirring state, be that the PVP solution 0.5ml of 10 g/L is added dropwise in the mixed solution 1 of palladium ion and chromium ion prepared above by concentration, obtain the mixed solution 2 of palladium ion, platinum ion and chromium ion;
随后称取0.03783g NaBH4放置于10ml水中形成NaBH4水溶液，取0.6ml NaBH4水溶液滴加入钯离子、铂离子和铬离子的混合溶液2中，继续搅拌30min得到深褐色的金属纳米胶体； Then weigh 0.03783g NaBH and place it in 10ml water to form NaBH aqueous solution, take 0.6ml NaBH aqueous solution and add dropwise in the mixed solution 2 of palladium ion, platinum ion and chromium ion, continue stirring for 30min to obtain dark brown metal nano colloid;
取0.5g CdS光催化剂，加入上述制备的金属纳米胶体中，并进行超声吸附30min，加入氨水调节溶液pH至8.2，将悬浊液过滤、洗涤、60℃烘干、研磨30min，得到负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂。 Take 0.5g of CdS photocatalyst, add it to the metal nanocolloid prepared above, and perform ultrasonic adsorption for 30min, add ammonia water to adjust the pH of the solution to 8.2, filter the suspension, wash, dry at 60°C, and grind for 30min to obtain the loaded Pt- CdS photocatalyst with Pd- Cr2O3 composite cocatalyst.
应用实施例1Application Example 1
负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂在光催化分解水制氢中的应用 Application of CdS Photocatalyst Supported Pt-Pd-Cr 2 O 3 Composite Co-catalyst in Photocatalytic Water Splitting for Hydrogen Production
称取40.2g亚硫酸铵于300ml水中，制备出1M 亚硫酸铵溶液（300mL），加入实施例1所制备的负载Pt-Pd-Cr2O3复合助催化剂的的CdS光催化剂0.5g,搅拌10分钟，随后转移至光催化反应器中，利用模拟太阳光，即采用Newport公司的1000W， 标定标准太阳光1.5AM的氙灯为光源，进行光催化制氢实验。最终结果见图1所示。从图1中可以看出，所制备的Pt-Pd-Cr2O3复合助催化剂可大幅提高CdS光催化分解水制氢活性。 Weigh 40.2g of ammonium sulfite in 300ml of water to prepare 1M ammonium sulfite solution (300mL), add 0.5g of CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite promoter prepared in Example 1, stir After 10 minutes, it was transferred to the photocatalytic reactor, and the photocatalytic hydrogen production experiment was carried out by using simulated sunlight, that is, a 1000W xenon lamp from Newport Company with a calibration standard sunlight of 1.5AM as the light source. The final result is shown in Figure 1. It can be seen from Figure 1 that the prepared Pt-Pd-Cr 2 O 3 composite co-catalyst can greatly improve the activity of CdS photocatalytic water splitting for hydrogen production.
对照实施例1Comparative Example 1
负载Pt助催化剂的CdS光催化剂的制备，步骤如下： The preparation of the CdS photocatalyst of supporting Pt promoter, the steps are as follows:
称取浓度为0.5g/L的氯铂酸水溶液5ml于10ml烧杯中，搅拌10min，得到铂离子溶液1; Take by weighing 5ml of chloroplatinic acid aqueous solution with a concentration of 0.5g/L in a 10ml beaker, stir for 10min to obtain platinum ion solution 1;
在不间断搅拌状态下，将浓度为10 g/L的PVP溶液0.5ml滴加入上述制备的钯离子溶液1中，得铂离子溶液2； Under uninterrupted stirring state, be that the PVP solution 0.5ml of 10 g/L is added dropwise in the palladium ion solution 1 of above-mentioned preparation by concentration, obtain platinum ion solution 2;
随后称取0.03783g NaBH4放置于10ml水中形成NaBH4水溶液，取0.8ml NaBH4水溶液滴加入上述的铂离子溶液2中，继续搅拌30min得到黑色的金属纳米胶体； Then weigh 0.03783g NaBH and place it in 10ml water to form NaBH aqueous solution, take 0.8ml NaBH aqueous solution and add it dropwise to the above-mentioned platinum ion solution 2 , and continue to stir for 30min to obtain black metal nanocolloid;
取0.5gCdS光催化剂，加入上述制备的金属纳米胶体中，并进行超声吸附30min，将悬浊液过滤、洗涤、60℃烘干、研磨得到有负载Pt助催化剂的CdS光催化剂。 Take 0.5g of CdS photocatalyst, add it to the metal nanocolloid prepared above, and carry out ultrasonic adsorption for 30min, filter the suspension, wash, dry at 60°C, and grind to obtain the CdS photocatalyst with Pt cocatalyst loaded.
对照实施例2Comparative Example 2
负载Pd助催化剂的CdS光催化剂的制备方法，步骤如下： The preparation method of the CdS photocatalyst of load Pd promoter, the steps are as follows:
称取浓度为0.5g/L的氯化钯水溶液5ml于10ml烧杯中，搅拌10min，得到钯离子溶液1; Take by weighing the palladium chloride aqueous solution 5ml that concentration is 0.5g/L in the 10ml beaker, stir 10min, obtain palladium ion solution 1;
于10ml烧杯中，在不间断搅拌状态下，将浓度为10 g/L的PVP溶液0.5ml滴加入上述制备的钯离子溶液1中，得钯离子溶液2； In a 10ml beaker, under continuous stirring, 0.5ml of PVP solution with a concentration of 10 g/L was added dropwise to the palladium ion solution 1 prepared above to obtain palladium ion solution 2;
随后称取0.03783g NaBH4放置于10ml水中形成NaBH4水溶液，取0.6ml NaBH4水溶液滴加入钯离子溶液2中，继续搅拌30min得到黑色的金属纳米胶体； Then weigh 0.03783g NaBH and place it in 10ml water to form NaBH aqueous solution, take 0.6ml NaBH aqueous solution and add it dropwise to palladium ion solution 2 , and continue to stir for 30min to obtain black metal nano colloid;
取0.5g CdS光催化剂，加入上述制备的金属纳米胶体中，并进行超声吸附30min，将悬浊液过滤、洗涤、60℃烘干、研磨得到负载有Pd助催化剂的CdS光催化剂。 Take 0.5g of CdS photocatalyst, add it to the metal nanocolloid prepared above, and perform ultrasonic adsorption for 30min, filter the suspension, wash, dry at 60°C, and grind to obtain the CdS photocatalyst loaded with Pd cocatalyst.
应用实施例2Application Example 2
将实施例1所得的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂,与对照实施例1所得的负载Pt助催化剂的CdS光催化剂和对照实施例2所得的负载Pd助催化剂的CdS光催化剂应用于光催化分解水制氢的反应，从而看出不同助催化剂的负载对CdS光催化剂光催化分解水制氢活性的影响。 With the load Pt-Pd-Cr of embodiment 1 gained O The CdS photocatalyst of composite promoter, the CdS photocatalyst of the load Pt promoter of comparative example 1 gained and the load Pd promoter of comparative example 2 gained CdS photocatalyst is applied to the reaction of photocatalytic water splitting to produce hydrogen, so that it can be seen that the loading of different co-catalysts affects the activity of CdS photocatalyst photocatalytically splitting water to produce hydrogen.
称取40.2g亚硫酸铵3份，分别于300ml水中，配置出1M 亚硫酸铵溶液（300 mL），再分别加入实施例1、对照实施例1及对照实施例2所制备的负载不同助催化剂的CdS光催化剂0.5g,转移至光催化反应器中，搅拌10分钟，随后转移至光催化反应器中，利用模拟太阳光，即采用Newport公司的1000W， 标定标准太阳光1.5AM的氙灯为光源，进行光催化制氢实验。结果见图2所示，从图2中可以看出不同助催化剂负载时，负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂在光催化分解水制氢活性远大于负载Pt的CdS光催化剂及负载Pd的CdS光催化剂催化活性。 Weigh 3 parts of 40.2g of ammonium sulfite, put them in 300ml of water respectively to prepare 1M ammonium sulfite solution (300 mL), then add the co-catalysts with different loads prepared in Example 1, Comparative Example 1 and Comparative Example 2 respectively 0.5g of CdS photocatalyst, transferred to the photocatalytic reactor, stirred for 10 minutes, then transferred to the photocatalytic reactor, using simulated sunlight, that is, using Newport’s 1000W, calibrated standard sunlight 1.5AM xenon lamp as the light source , for photocatalytic hydrogen production experiments. The results are shown in Figure 2. It can be seen from Figure 2 that the CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite co-catalyst has a much higher hydrogen production activity in photocatalytic water splitting than the CdS loaded with Pt when different co-catalysts are loaded. Photocatalyst and catalytic activity of CdS photocatalyst loaded with Pd.
实施例2Example 2
Pt含量按其相当于CdS光催化剂重量的0.1wt.%的负载Pt-Pd-Cr2O3复合 The Pt content is equivalent to 0.1wt.% of the weight of the CdS photocatalyst. The supported Pt-Pd-Cr 2 O 3 composite
助催化剂的CdS光催化剂的制备，步骤如下： The preparation of the CdS photocatalyst of promoter, the steps are as follows:
称取浓度为1g/L的氯化钯水溶液2ml、浓度为0.5g/L的氯铂酸水溶液1ml以及浓度为0.5g/L的硝酸铬水溶液0.5ml，搅拌10min，得到钯离子、铂离子和铬离子的混合溶液1； Taking by weighing concentration is 1g/L palladium chloride aqueous solution 2ml, concentration is the chloroplatinic acid aqueous solution 1ml of 0.5g/L and concentration is the chromium nitrate aqueous solution 0.5ml of 0.5g/L, stirs 10min, obtains palladium ion, platinum ion and Chromium ion mixed solution 1;
在不间断搅拌状态下，将10 g/L的PVP溶液0.5ml滴加入上述制备的钯离子、铂离子和铬离子的混合溶液1中，得钯离子、铂离子和铬离子的混合溶液2； Under uninterrupted stirring state, the PVP solution 0.5ml of 10 g/L is added dropwise in the mixed solution 1 of palladium ion, platinum ion and chromium ion prepared above, obtains the mixed solution 2 of palladium ion, platinum ion and chromium ion;
随后称取0.03783g NaBH4放置于10ml水中形成NaBH4水溶液，取1ml NaBH4水溶液滴加入到上述的钯离子、铂离子和铬离子的混合溶液2中，继续搅拌30min得到深褐色的金属纳米胶体； Then weigh 0.03783g NaBH and place it in 10ml water to form NaBH aqueous solution, add 1ml of NaBH aqueous solution dropwise to the mixed solution 2 of palladium ion, platinum ion and chromium ion, continue stirring for 30min to obtain dark brown metal nano colloid ;
取0.5g CdS光催化剂，加入上述制备的金属纳米胶体中，加入氨水调节溶液pH至8.2，并进行超声吸附30min，将悬浊液过滤、洗涤、60℃烘干、研磨得到Pt含量按其相当于CdS光催化剂重量的0.1wt.%的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂。 Take 0.5g of CdS photocatalyst, add it to the metal nanocolloid prepared above, add ammonia water to adjust the pH of the solution to 8.2, and perform ultrasonic adsorption for 30min, filter the suspension, wash, dry at 60°C, and grind to obtain the Pt content according to its equivalent CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite cocatalyst at 0.1wt.% of the weight of CdS photocatalyst.
实施例3Example 3
Pt含量按其相当于CdS光催化剂重量的0.2wt.%的负载Pt-Pd-Cr2O3复合 The Pt content is equivalent to 0.2wt.% of the weight of the CdS photocatalyst. The supported Pt-Pd-Cr 2 O 3 composite
助催化剂的CdS光催化剂的制备，步骤如下： The preparation of the CdS photocatalyst of promoter, the steps are as follows:
步骤（1）中的浓度为0.5g/L的氯铂酸水溶液取2ml，其他均同实施例2，最终得到Pt含量按其相当于CdS光催化剂重量的0.2wt.%的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂。 Concentration in the step (1) is that the chloroplatinic acid aqueous solution of 0.5g/L gets 2ml, and others are all the same as embodiment 2, finally obtains the loaded Pt-Pd- CdS photocatalyst with Cr2O3 composite cocatalyst .
实施例4Example 4
Pt含量按其相当于CdS光催化剂重量的0.3wt.%的负载Pt-Pd-Cr2O3复合 The Pt content is equivalent to 0.3wt.% of the weight of the CdS photocatalyst. The supported Pt-Pd-Cr 2 O 3 composite
助催化剂的CdS光催化剂的制备，步骤如下： The preparation of the CdS photocatalyst of promoter, the steps are as follows:
步骤（1）中的浓度为0.5g/L的氯铂酸水溶液取3ml，其他均同实施例2，最终得到Pt含量按其相当于CdS光催化剂重量的0.3wt.%的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂。 Concentration in the step (1) is that 0.5g/L aqueous solution of chloroplatinic acid gets 3ml, and others are all the same as embodiment 2, finally obtains the loaded Pt-Pd- CdS photocatalyst with Cr2O3 composite cocatalyst .
实施例5Example 5
Pt含量按其相当于CdS光催化剂重量的0.4wt.%的负载Pt-Pd-Cr2O3复合 The Pt content is equivalent to 0.4wt.% of the weight of the CdS photocatalyst. The supported Pt-Pd-Cr 2 O 3 composite
助催化剂的CdS光催化剂的制备，步骤如下： The preparation of the CdS photocatalyst of promoter, the steps are as follows:
步骤（1）中的浓度为0.5g/L的氯铂酸水溶液取4ml，其他均同实施例2，最终得到Pt含量按其相当于CdS光催化剂重量的0.4wt.%的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂。 Concentration in the step (1) is that the aqueous solution of 0.5g/L chloroplatinic acid gets 4ml, and others are all the same as embodiment 2, finally obtains the loaded Pt-Pd- CdS photocatalyst with Cr2O3 composite cocatalyst .
对照实施例3Comparative Example 3
Pt含量为0时，即负载Pd-Cr2O3复合助催化剂的CdS光催化剂的制备，步骤如下： When the Pt content is 0, that is, the preparation of the CdS photocatalyst supporting the Pd-Cr 2 O 3 composite co-catalyst, the steps are as follows:
步骤（1）中的浓度为0.5g/L的氯铂酸水溶液取0ml，其他均同实施例2，最终得到Pt含量为0的负载Pd-Cr2O3复合助催化剂的CdS光催化剂。 In step (1), 0ml of chloroplatinic acid aqueous solution with a concentration of 0.5g/L was taken, and the others were the same as in Example 2, and finally a CdS photocatalyst loaded with a Pd-Cr 2 O 3 composite co-catalyst with a Pt content of 0 was obtained.
应用实施例2Application Example 2
应用实施例2、3、4、5及对照实施例3所得的不同的Pt负载量的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂进行光催化分解水制氢活性的影响分析 The impact analysis of the CdS photocatalyst of the load Pt-Pd-Cr 2 O 3 composite promoters of the different Pt loadings obtained in Examples 2, 3, 4, 5 and Comparative Example 3 to carry out photocatalytic decomposition of water for hydrogen production
分别称取40.2g亚硫酸铵5份，分别于300ml水中，配置出1M 亚硫酸铵溶液（300 mL）5份，分别加入实施例2、3、4、5及对照实施例3所得的不同的Pt负载量的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂0.5g，搅拌10分钟，随后转移至光催化反应器中，利用模拟太阳光，即采用Newport公司1000W，标定标准太阳光1.5AM的氙灯为光源，进行光催化制氢实验。最终结果见图3及图4所示，从图3及图4中可以看出，不同的Pt负载量的负载Pt-Pd-Cr2O3复合助催化剂的CdS光催化剂对CdS光催化剂光催化分解水制氢活性的影响较大，当Pt的添加量为CdS光催化剂质量的0.3wt.%时，CdS光催化剂光催化制氢活性最高，此时制氢光量子效率可达50.5%（420nm可见光照射时）。 Weigh 5 parts of 40.2g ammonium sulfite respectively, put them in 300ml water respectively, configure 5 parts of 1M ammonium sulfite solution (300 mL), add the different ammonium sulfite obtained in Examples 2, 3, 4, 5 and Comparative Example 3 respectively 0.5g of CdS photocatalyst loaded with Pt-Pd-Cr 2 O 3 composite co-catalyst, stirred for 10 minutes, then transferred to a photocatalytic reactor, using simulated sunlight, that is, 1000W from Newport Company, to calibrate the standard solar The light 1.5AM xenon lamp was used as the light source, and the photocatalytic hydrogen production experiment was carried out. The final results are shown in Figure 3 and Figure 4. It can be seen from Figure 3 and Figure 4 that the CdS photocatalysts loaded with Pt-Pd-Cr 2 O 3 composite co-catalysts with different Pt loadings have a greater effect on the photocatalysis of CdS photocatalysts. The hydrogen production activity of water splitting has a great influence. When the amount of Pt added is 0.3wt.% of the mass of the CdS photocatalyst, the CdS photocatalyst has the highest photocatalytic hydrogen production activity. At this time, the photoquantum efficiency of hydrogen production can reach 50.5% (420nm visible light during irradiation).
上述具体实施例只是用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利保护范围内，对本发明做出的任何修改和改变，都落入本发明的保护范围。 The specific embodiments above are only used to explain the present invention, rather than to limit the present invention. Within the spirit and scope of protection of the present invention, any modifications and changes made to the present invention will fall within the protection scope of the present invention.
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| CN115582119A (en) * | 2022-10-28 | 2023-01-10 | 陕西科技大学 | A kind of cerium-doped bismuth tungstate supported platinum/chromium trioxide photocatalytic hydrogen production material and preparation method thereof |
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Application publication date: 20120104 |