本文選題：光催化技術(shù) + ZnO��； 參考：《江蘇大學(xué)》2017年碩士論文

【摘要】：光催化技術(shù)不僅是一種具有易于操作和可完全降解有機(jī)物分子等優(yōu)點(diǎn)的高級(jí)氧化法,也是一項(xiàng)利用光能來降解有機(jī)污染物的綠色環(huán)保技術(shù)。在眾多催化劑中,ZnO是一種寬禁帶(約為3.37 eV)直接帶隙n型半導(dǎo)體材料,因其具有來源豐富、價(jià)格低廉、化學(xué)穩(wěn)定性好、熱穩(wěn)定性高和無毒等優(yōu)點(diǎn),使得其在光催化劑的研究中備受關(guān)注。但是,ZnO的帶隙較寬,使得其對(duì)太陽能的利用效率較低,光生載流子的復(fù)合率高,量子效率低,大大限制了ZnO的應(yīng)用。基于ZnO光催化劑在應(yīng)用過程中存在的這些問題,本論文中我們采用了一系列改性方法合成了氧化鋅基光催化劑。利用半導(dǎo)體間電子轉(zhuǎn)移過程原理構(gòu)建異質(zhì)結(jié)型復(fù)合光催化劑,采用具有合適的導(dǎo)帶和價(jià)帶位置的CeO_2來與ZnO耦合,以埃洛石納米管(HNTs)為載體,通過濕法煅燒制得ZnO/CeO_2@HNTs異質(zhì)結(jié)光催化劑;利用碳量子點(diǎn)(CQDs)獨(dú)特的光學(xué)特性設(shè)計(jì)量子點(diǎn)敏化型復(fù)合光催化劑,以埃洛石納米管為載體,制備CQDs/ZnO@HNTs復(fù)合光催化劑;利用貴金屬的等離子體共振效應(yīng),通過其電荷傳輸和能量傳遞來提高光利用率和降低光生載流子的復(fù)合率,構(gòu)筑具有等離子體效應(yīng)的碳參雜氧化鋅殼-銀核結(jié)構(gòu)的Ag@ZnO/C復(fù)合光催化劑;利用溫敏聚合物獨(dú)特的溫度響應(yīng)性親疏水功能設(shè)計(jì)出ZnO/C表面接枝聚(N-異丙基丙烯酰胺)(PNIPAM)溫敏響應(yīng)聚合物,獲得溫敏型智能識(shí)別選擇性降解功能的復(fù)合光催化材料。具體內(nèi)容如下:以埃洛石納米管為載體,通過濕法煅燒制備了星云狀ZnO/CeO_2@HNTs異質(zhì)結(jié)納米復(fù)合光催化劑。采用透射電鏡(TEM)、高倍透射電鏡(HRTEM)、X射線衍射儀(XRD)、紅外光譜儀(FT-IR)、紫外-可見光漫反射儀(UV-vis DRS)、X射線光電子能譜儀(XPS)、電化學(xué)測(cè)試等表征手段對(duì)材料進(jìn)行表征。在模擬太陽光的照射下,通過降解四環(huán)素水溶液來測(cè)試樣品的光催化活性。從表征結(jié)果中可以得到:濕法煅燒過程中,水分子為氧化物的形成提供了充足的氧源,在水分的快速蒸發(fā)過程中,促使星云狀的ZnO/CeO_2納米簇的形成。當(dāng)Zn:Ce摩爾比為3:1,煅燒溫度為500℃,氧化物:載體的質(zhì)量比為1:1時(shí),制備出的光催化劑對(duì)四環(huán)素呈現(xiàn)出了最好的光降解率,60 min內(nèi)其光降解率可達(dá)到87%。以檸檬酸和乙二胺為原料,利用微波法制備出碳量子點(diǎn)(CQDs)溶液。以氯化鋅、氫氧化鋰為原料,以HNTs為載體,以乙醇為溶劑,通過超聲-沉淀法制得ZnO@HNTs納米復(fù)合前軀體。通過二次水熱制備CQDs/ZnO@HNTs量子點(diǎn)敏化復(fù)合光催化劑。通過TEM、XRD、FT-IR、UV-vis DRS、XPS、電化學(xué)測(cè)試等表征手段對(duì)材料進(jìn)行表征,通過在可見光下降解四環(huán)素來考察所得催化劑的活性。實(shí)驗(yàn)結(jié)果表明:CQDs成功修飾于分散性良好的ZnO@HNTs前軀體表面,并且增強(qiáng)了可見光下的催化活性。采用葡萄糖為碳源,以醋酸鋅、硝酸銀、氫氧化鋰為原料,以乙二醇為溶劑,經(jīng)過一步還原制得Ag納米粒子,通過溶劑熱法形成ZnO納米粒子包裹Ag核結(jié)構(gòu),制得Ag@ZnO/C等離子體效應(yīng)核殼型復(fù)合光催化劑。通過掃描電鏡(SEM)、X射線能譜儀(EDS)、TEM、XRD、FT-IR、UV-vis DRS、XPS、電化學(xué)測(cè)試等對(duì)所制備材料進(jìn)行表征,并通過降解四環(huán)素來考察催化劑的性能。結(jié)合表征結(jié)果可以得到:當(dāng)ZnO:Ag摩爾比為5:1,葡萄糖用量為0.4 g時(shí),樣品降解效果最好,降解率可達(dá)到82.2%。此外,結(jié)合電子自旋共振圖譜分析(ESR),基于ZnO殼-Ag核結(jié)構(gòu)和等離子體共振效應(yīng),提出了可能的反應(yīng)機(jī)理。以N-異丙基丙烯酰胺(NIPAM)為溫敏功能單體,N’N-亞甲基雙丙烯酰胺(MBA)為交聯(lián)劑,過硫酸銨(APS)為引發(fā)劑,通過3-(異丁烯酰氧)丙基三甲氧基硅烷(MPS)對(duì)ZnO/C前軀體進(jìn)行表面修飾并接枝溫敏聚合物,合成了PNIPAM@ZnO/C溫敏響應(yīng)功能化光催化劑。用SEM、EDS、XRD、FT-IR、UV-vis DRS等測(cè)試手段對(duì)復(fù)合光催化劑進(jìn)行表征,并通過光催化降解四環(huán)素溶液來考察其催化活性。結(jié)果顯示,在高溫下(45℃),催化劑活性受到抑制;在低溫下(20℃),催化劑表現(xiàn)出良好的催化活性。PNIPAM修飾的ZnO/C復(fù)合智能光催化劑具有良好的溫度響應(yīng)性能和光催化降解活性,達(dá)到了溫度調(diào)節(jié)控制降解活性的功能化要求。
[Abstract]:Photocatalytic technology is not only a kind of advanced oxidation method, which has the advantages of easy to operate and completely degrade organic molecules, but also a green technology to degrade organic pollutants by using light energy. In many catalysts, ZnO is a kind of wide band gap (about 3.37 eV) direct band gap n semiconductor material, because of its rich source and price. Low lattice, good chemical stability, high thermal stability and non-toxic and so on, it has attracted much attention in the study of photocatalyst. However, ZnO has a wide band gap, which makes the utilization of solar energy low, the recombination rate of light carrier is high, and the quantum efficiency is low. The application of the ZnO photocatalyst in the application process is based on the large limit of the application of the photocatalyst in the application process. In this paper, we used a series of modified methods to synthesize the Zinc Oxide based photocatalyst, using the principle of electron transfer between semiconductors to construct a heterojunction composite photocatalyst, coupled with ZnO with a suitable guide band and valence band position CeO_2, and using the HNTs as the carrier and wet calcined by wet method. The ZnO/CeO_2@HNTs heterojunction photocatalyst was prepared, and a quantum dot sensitized composite photocatalyst was designed by using the unique optical properties of carbon quantum dots (CQDs). The CQDs/ZnO@HNTs composite photocatalyst was prepared by using the yallot nanotube as the carrier, and the use of the plasma resonance effect of precious metals was used to improve the optical utilization by its charge transfer and energy transfer. The Ag@ZnO/C composite photocatalyst of a carbon mixed Zinc Oxide shell and silver nucleus with plasma effect was constructed by rate and reduction of the recombination rate of the photogenerated carrier, and a thermosensitive intellect was obtained by using the unique temperature responsive hydrophobicity of the thermosensitive polymers to graft poly (N- isopropyl acryl amine) (PNIPAM) Wen Min response polymer on the surface of ZnO/C. The composite photocatalyst can be used to identify the selective degradation function. The contents are as follows: the nano composite photocatalyst of nebulous ZnO/CeO_2@HNTs heterojunction was prepared by wet calcination with the hydrometallurgy of the eno nanotube. Using transmission electron microscope (TEM), high transmission electron microscope (HRTEM), X ray diffractometer (XRD), infrared spectrometer (FT-IR), UV visible The material is characterized by UV-vis DRS, X ray photoelectron spectroscopy (XPS) and electrochemical measurement. The photocatalytic activity of the sample is tested by the degradation of the tetracycline water solution under the irradiated sunlight. The water molecules can be obtained from the characterization results as the formation of the oxide in the process of wet calcination. A sufficient oxygen source promotes the formation of a nebula like ZnO/CeO_2 nanocluster in the process of rapid evaporation of water. When the Zn:Ce molar ratio is 3:1, the calcining temperature is 500, and the mass ratio of the carrier is 1:1, the prepared photocatalyst presents the best light degradation rate to tetracycline, and the photodegradation rate can reach 87%. with citric acid within 60 min. Carbon quantum dots (CQDs) solution was prepared by microwave method with ethylenediamine as raw material. Using zinc chloride and lithium hydroxide as raw material, HNTs as the carrier and ethanol as solvent, the ZnO@HNTs nanocomposite precursor was obtained by ultrasonic precipitation method. The CQDs/ZnO@HNTs quantum dot sensitized composite photocatalyst was prepared by two times of water heat. Through TEM, XRD, FT-IR, UV-vis D RS, XPS, electrochemical testing and other characterization methods were used to characterize the material, and the activity of the catalyst was investigated by degradation of tetracycline under visible light. The results showed that CQDs was successfully modified on the well dispersed ZnO@HNTs precursor surface and enhanced the catalytic activity under visible light. The Ag nanoparticles were prepared by one step reduction by one step reduction of lithium hydroxide as the raw material. ZnO nanoparticles were formed by solvent thermal method to wrap the Ag nuclear structure. The Ag@ZnO/C plasma effect nuclear shell composite photocatalyst was prepared. By scanning electron microscope (SEM), X ray energy spectrometer (EDS), TEM, XRD, FT-IR, UV-vis DRS, electrochemical testing and so on, The prepared materials were characterized, and the performance of the catalyst was investigated by degradation of tetracycline. When the ZnO:Ag molar ratio was 5:1 and the amount of glucose was 0.4 g, the degradation efficiency was best, the degradation rate could reach 82.2%., combined with the electron spin resonance spectrum analysis (ESR), based on the ZnO shell -Ag nuclear structure and plasma. The possible reaction mechanism was proposed, with N- isopropyl acrylamide (NIPAM) as thermosensitive monomer, N 'N- methylene diacrylamide (MBA) as crosslinking agent, ammonium persulfate (APS) as initiator, and 3- (isobutylyl) propyl trimethoxy silane (MPS) on the surface modification of the ZnO/C precursor and grafting of temperature sensitive polymers. PNIPAM@ZnO/C thermosensitive functionalized photocatalyst was used to characterize the composite photocatalyst with SEM, EDS, XRD, FT-IR, UV-vis DRS and so on. The catalytic activity of the catalyst was investigated by photocatalytic degradation of tetracycline solution. The results showed that the activity of the catalyst was inhibited at high temperature (45 C), and the catalyst was good at low temperature (20 degrees C). A good catalytic active.PNIPAM modified ZnO/C composite photocatalyst has good temperature response and photocatalytic degradation activity, which has achieved the functional requirements of temperature regulation to control degradation activity.

【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703;O643.36

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