CN111072056B - Liquid-phase CdS nanorod size-controlled growth method - Google Patents
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Abstract
本发明涉及新型液相体系中CdS纳米材料的合成方法，实现了CdS纳米棒在合成过程中对尺寸的更为简单有效的控制，具体制备为将50～65mg质量的CdO、250～334mg质量的ODPA、55～125mg质量的HPA和3～5g质量的TOPO置于容器内，在氩气环境下除氧，此时温度为100～120℃，30～60分钟后，将混合物加热到260～300℃至溶液完全澄清透明，注入0.8～1.2ml TOP；之后将混合物升温至350～360℃，在此温度下，注入0.8～1ml S前驱体(0.2～0.25mol/L，S的ODE溶液)和50～60nmol CdS晶种；反应时间5秒～11分钟，可得长度5～150nm的纳米棒，生长时间越长，纳米棒越长。
The invention relates to a method for synthesizing CdS nanomaterials in a novel liquid phase system, which realizes simpler and more effective control of the size of CdS nanorods in the synthesis process. ODPA, 55-125 mg of HPA and 3-5 g of TOPO are placed in a container, deoxygenated in an argon atmosphere, the temperature at this time is 100-120 ° C, and after 30-60 minutes, the mixture is heated to 260-300 ℃ until the solution is completely clear and transparent, inject 0.8～1.2ml TOP; then the mixture is heated to 350～360℃, at this temperature, inject 0.8～1ml S precursor (0.2～0.25mol/L, ODE solution of S) and 50-60 nmol CdS seeds; the reaction time is 5 seconds-11 minutes, and nanorods with a length of 5-150 nm can be obtained, and the longer the growth time, the longer the nanorods.
Description
Technical Field
The invention relates to a method for synthesizing a CdS nano material in a novel liquid phase system, which realizes simpler and more effective control of the CdS nano rod on the size in the synthesis process.
Background
Currently, the global Energy supply is mainly from fossil fuels, (ref 1: EIA, International Energy Outlook 2016.) however, due to the problems of limited reserves and environmental pollution, the Energy supply structure is gradually transformed, wherein the utilization and transformation of solar Energy is the hot direction of the current research and application. (reference 2: EIA, International Energy Outlook 2017.) in solar Energy utilization, semiconductor nanomaterials mainly play the role of light Energy collectors and converters. (references 3-4: Cells, Q.D.S., Semiconductor Nanocrystals as Light Harvesters Kamat, prashan's V.journal of Physical Chemistry C,2008.112(48): p.18737-18753.; Chica, B.et al, Balancing electron transfer and driving for effective photocatalytic hydrogen production in CdSe/CdS nanorod [ NiFe ] hydrogen evolution. energy & Environmental Science,2017.10(10): p.2245-2255.) in recent years, CdS nanorods have been found to have excellent optoelectronic properties, both in terms of solar hydrogen production and in terms of potential for solar Cells. (see references 4-7: Chinese, B., et al, balance electronic transmission and transmission for electronic purposes in CdSe/CdS Nano- [ NiFe ] hydrogenesis assemblies, energy & Environmental Science,2017.10(10): p.2245-2255.; Wu, K., et al, impact Extraction of translated Holes Chemical Society, Journal of American Chemical Society,2015.137(32): p.10224-10230.; Achtstein, A.W. I., absorption, B.S. 0. D,1D, 2D. and P.2 D.S. 3. and P.S.76. J.P.S. 76, P.S. 7678; Journal of gold, P.S.S. 76, P.S.P.F.76, P.S.P.P.76, P.S.P.P.P.S. 76, P.S.S. 76, P.S.P.S.P.S.P.S. 76, P.S.S. 76, P.S.P.P.S. 76, P.S.S.S.P.P.S. 76, P.S. 76, P.S.S. 76, P.S.P.S. 76, P.S. 76, P.P.S.S. 76, P.S.S. I. 76, P.P.P.S. I. P.S. 76, P.S. 76, P.S. P.P.P.S. 76, P.S. 76, P.P.S. P.S. P.P.S. 76, P.S. 76, P.S. P.P.S. P.S. 76, P.S. No. P.P.S. P.S. P.P.P.S. P.S. 76, P.S. P.P.P.P.P.S. P.P.P.P.P.P.P.S. P.P.S. P.S. P.P.S. P.P.P.S. P.P.S. P.S. P.P.P.S. P.P.S. P.S. P.P.P.S. P.P. P.S. P.P.P.S. P.P.S. P.S. P.P.S. P.P.P.P.P.P.S. P.P.P.P.S. P.P.P.S. P.P.P.P.P.P.P.P.S. P.S. P.P.P.P.P.P.P.S. P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.P.S. P.S. P.P.S. P.P.P.S. P.S. P.P.P.S, due to quantum effects, the size of the nanorods has a great influence on the conversion efficiency of light energy. (reference 8-11: Padiha, L.A., et al., Aspect ratio dependence of auto-synthesis and carrier multiplication in PbSe nanoparticles, Nano Lett,2013.13(3): p.1092-9.; Zhu, H.et al., Near unity quality of light-drive red medium reduction and efficiency H2generation using colloidal nano-crystalline colloidal gold nanoparticles, 2012.134(28): p.11701-8.; Wu, K.and T.Lian, Quantum synthetic colloidal gold nanoparticles for colloidal-to-chemical chemistry, Scirkun.3. CdS-75. Cdson-K.and T.S.A. and Cdse.S.A. Pat. No. 3. Cdsn.3. Cdso.S. Cdso.S.A. Cdso.S.S. for colloidal-to-chemical chemistry, Cdsn.S.S.S.3. Cdsn.S. Pat. No. 11. Cdsn.S.3. Cdso.A. Cdso.S. Pat. 3. Cdso.A. Cdso.S. No. Cdso.3. Cdso.A. Cdso.S. Cdso.A. Pat. No. 3. Cdso.3. Cdso.A. 3. Cdso.A. Cdso.A.A. Cdso.A. No. Cdso.A. Cdsof Cdso. Cdso.A. 7.A.A.A. No. 7, et al, et.A. No. Cdso.A. Cdso.A.A.A. No. 3, et.A.A. No. 7, et al, et.A.A. Cdso. 2, whereby CdS. Cdso.A. No. Cdso.A. Cdso. Cdso.A.A.A.A. Cdso.A.A.A.A.A.A.A. No. Cdso.A.A.A.A. No. 7, et al, whereby CdS. Cdso.A. 7, whereby CdS. Cdso. Cdso.A. Cdso. Cdso.A. Cdso. Cdso.A. is a. Cdso..
In scientific research, in order to comparatively study the size effect of nanorods, it is generally required to synthesize nanorod materials having the same diameter, different lengths, or different diameters and the same length. However, the nanorods synthesized by the existing method are longer, the diameter is increased, and the diameter can hardly be controlled to be kept unchanged. When the nano-rods with the constant diameter and the longer length are required to grow, the proportion of the ligand and the synthesis conditions need to be changed. Thus, the cost and complexity of synthesizing nanorods with different size requirements are increased, and therefore, a simpler and more effective method for controlling the synthesis of nanorods is needed.
Disclosure of Invention
According to the current requirements on nano rod materials and the technical defects, the invention provides a method for synthesizing a liquid-phase CdS nano rod. ODPA (n-octadecylphosphonic acid) and HPA (hexylphosphinic acid) are selected as ligands for nanorod growth, a proper raw material ratio is found, and the experimental process is improved. Under the condition, the diameter of the synthesized nanorod can be kept unchanged, and the CdS nanorods with different lengths can be obtained only by regulating and controlling the growth time.
A method for synthesizing a liquid-phase CdS nanorod with accurate and controllable size,
placing 50-65 mg of CdO, 250-334 mg of ODPA, 55-125 mg of HPA and 3-5 g of TOPO in a container, deoxidizing in an argon environment, heating the mixture to 260-300 ℃ after 30-60 minutes at the temperature of 100-120 ℃ until the solution is completely clear and transparent, and injecting 0.8-1.2 ml of TOP; then heating the mixture to 350-360 ℃, and injecting 0.8-1 ml of S precursor (0.2-0.25 mol/L, ODE solution of S) and 50-60 nmol of CdS seed crystal at the temperature;
the reaction time is 5 seconds to 11 minutes, the nano rod with the length of 5nm to 150nm can be obtained, and the longer the growth time is, the longer the nano rod is.
The diameter size of the nano-rod is determined by the proportion of the ligand components in the solution, and the specific parameters are as follows: ODPA: HPA (molar concentration) ═ 1.8: 1, the diameter size of the nano rod is about 3.4 +/-0.4 nm; when ODPA: when the molar concentration ratio of HPA is increased (1.0-3.0), the diameter size of the nano-rod is increased (2.8-5.0 nm).
The length of the nanorod is changed by changing the growth time, the nanorod with the length of 5-150 nm can be synthesized by the growth time from 5 seconds to 11 minutes, and the longer the growth time is, the longer the nanorod is.
The synthesis method of the CdS seed crystal comprises the following steps: weighing 50-60 mg of CdO (cadmium oxide), 0.15-0.20 ml of OA and 5-8 ml of ODE, placing the mixture in a container, and deoxidizing for 30-60 minutes in an argon environment, wherein the temperature is 100-120 ℃; then heating the mixture to 260-300 ℃, and injecting 1-1.5 ml of TOP when CdO is completely dissolved to obtain a clear and transparent solution; cooling the solution to 220-260 ℃; injecting 0.8-1 ml S (sulfur) precursor (0.2-0.25 mol/L, ODE solution of S) and violently stirring; maintaining for 40 seconds to 3 minutes, and placing the container in an ice bath for cooling to obtain the CdS seed crystal with the diameter range of 2.6 to 8.6 nm.
The diameter and size of the nano-rod can be controlled by regulating the proportion of different ligands in the solution; under the condition of determining the system components, the change of the length of the nano rod can be realized by changing the growth time, and the diameter of the nano rod is kept unchanged. The ligand molecules with different proportions directly determine the diameter size of the nano-rod, because the long-chain acid molecules are adsorbed on the surface of the seed crystal, and have control effect on the crystalline phase and the growth direction of the seed crystal.
Under the condition of a certain ligand proportion, the diameter size of the nanorod is determined, the length of the nanorod can be changed by only changing the growth time, the longer the nanorod is, if the nanorod with different length is needed, the nanorod with different length can be extracted in the corresponding growth time, the raw materials do not need to be reconfigured for re-synthesis, and the synthesis method with the time-controlled length can improve the synthesis efficiency.
Drawings
The principle and specific process of the present invention will be described in detail below with reference to the accompanying drawings.
FIG. 1 is a schematic view of the synthetic process of CdS nanorods and a transmission electron microscope picture of the CdS nanorods at different growth times (45s, 2.5min, 3.5 min).
Wherein: the synthesis method adopts a seed crystal growth method, CdS seed crystals are synthesized firstly, and then long-chain acid with a specific proportion is matched to control the growth direction of nanorod crystals. After different growth time, CdS nanorods with similar diameters and different lengths can be obtained.
FIG. 2 is the UV-VIS absorption spectra of three synthesized nanorods with different lengths.
The position of the first exciton peak (absorption peak at 450nm in the figure) in the ultraviolet visible absorption spectrum represents the quantum confinement degree of the nanorod in the diameter direction, and the positions of the first exciton absorption peaks of the nanorods with the three lengths are similar, which shows that the quantum effects of the nanorods in the diameter direction are similar, and proves that the nanorods with the three lengths have similar diameters.
FIG. 3 shows the length distribution statistics of CdS nanorods.
Detailed Description
Example 1
First, we need to synthesize CdS seeds: 50.0mg of CdO (cadmium oxide), 0.18ml of OA (oleic acid) and 5ml of ODE (1-octadecene ) were weighed into a three-necked flask, deoxygenated under argon atmosphere for one hour, at which time the temperature was set to 120 ℃; the mixture was then heated to 300 ℃ and when the CdO had completely dissolved, a clear and transparent solution was obtained, and 1.5ml of TOP (trioctylphosphine, tri-n-octylphosphine) was injected. Because TOP is injected, the temperature of the solution can be reduced to about 260 ℃, and the heating device is closed to continue reducing the temperature, so that the temperature of the solution is reduced to 250 ℃. At this point 0.8ml of S (sulphur) precursor (0.25mol/L, ODE solution of S) was injected rapidly and stirred vigorously. Maintaining for 40s, removing the heating jacket, placing the three-necked flask in an ice bath for rapid cooling to obtain CdS seed crystal with diameter of about 2.6 nm.
The synthetic process of the CdS nanorod comprises the following steps: 58mg of CdO, 290mg of ODPA (n-octadecylphosphonic acid, n-octadecyl phosphate), 80mg of HPA (hexylphosphinic acid, n-hexylphosphoric acid) and 3g of TOPO (trioctylphosphine oxide, tri-n-octylphosphine oxide) were weighed into a 25ml three-necked flask and deoxygenated under an argon atmosphere, at which time the temperature was set at 120 ℃. After one hour, the mixture was heated to 300 ℃ until the solution was completely clear and transparent, and 0.8ml of TOP was injected. The mixture was then warmed to 350 ℃ at which temperature 0.8ml of S precursor (0.25mol/L, ODE solution of S) and CdS seeds (55nmol) were injected rapidly. After different growth time, the nano rods with different lengths and diameters of 3.4 +/-0.4 nm can be obtained, and the longer the growth time is, the longer the nano rods are. The specific results are shown in FIGS. 1-3.
Example 2
The operation process is the same as that of the embodiment 1, and is different from that of the embodiment 1 in that: in the raw material ratio of the synthesized nano-rod in the embodiment 1, ODPA: HPA (molar concentration) ═ 1.8: 1, when the dosage and the molar concentration of CdO, S, TOP, CdS seed crystal and TOPO in the system are kept unchanged, the ODPA: molar ratio of HPA to 2.2: at 1 (HPA molar concentration in the system is unchanged), the diameter of the CdS nanorod is increased to 4.1 nm.
Claims (2)
1. A method for synthesizing a liquid-phase CdS nanorod with accurate and controllable size,
placing 50-65 mg of CdO, 250-334 mg of ODPA, 55-125 mg of HPA and 3-5 g of TOPO in a container, deoxidizing in an argon environment, heating the mixture to 260-300 ℃ after 30-60 minutes at the temperature of 100-120 ℃ until the solution is completely clear and transparent, and injecting 0.8-1.2 ml of TOP; then heating the mixture to 350-360 ℃, and injecting 0.8-1 ml of S precursor and 50-60 nmol of CdS seed crystal at the temperature, wherein the precursor is 0.2-0.25 mol/L ODE solution of S;
the specific parameters are as follows:
when ODPA: when the molar concentration ratio of HPA is increased between 1.0 and 3.0, the diameter size of the nanorod is increased within the range of 2.8 to 5.0 nm;
when ODPA: molar ratio of HPA = 1.8: when 1, the diameter size of the nano rod is 3.4 +/-0.4 nm; the length of the nanorod is changed by changing the growth time, the nanorod with the length of 5-150 nm can be synthesized by the growth time from 5 seconds to 11 minutes, and the longer the growth time is, the longer the nanorod is.
2. The method of synthesis according to claim 1,
the synthesis method of the CdS seed crystal comprises the following steps: weighing 50-60 mg of CdO (cadmium oxide), 0.15-0.20 ml of OA and 5-8 ml of ODE, placing the mixture in a container, and deoxidizing for 30-60 minutes in an argon environment, wherein the temperature is 100-120 ℃; then heating the mixture to 260-300 ℃, and injecting 1-1.5 ml of TOP when CdO is completely dissolved to obtain a clear and transparent solution; cooling the solution to 220-260 ℃; when the temperature is adjusted to 240-250 ℃, 0.8-1 ml of S (sulfur) precursor is injected and stirred vigorously; maintaining for 40 seconds to 3 minutes, and placing the container in an ice bath for cooling to obtain the CdS seed crystal with the diameter range of 2.6 to 8.6 nm.
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