本文關(guān)鍵詞：微波法制備金屬磷酸鹽及其光催化性能研究　出處：《東華大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 微波法 磷酸鈷 羥基磷酸銅 磷酸鋯鈷 光催化性能 機(jī)理

【摘要】：本文主要通過微波輔助加熱法在低溫常壓的條件下制備了三種金屬磷酸鹽材料,包括磷酸鈷、羥基磷酸銅以及磷酸鋯鈷,并通過XRD、SEM、TEM、FT-IR、Raman、TG、DRS和SPV等手段對(duì)材料的物相、形貌、熱穩(wěn)定性及光電學(xué)性質(zhì)進(jìn)行研究。將三種磷酸鹽作為非均相催化劑應(yīng)用于印染廢水處理中,研究了形貌和制備條件等內(nèi)部因素以及催化劑和雙氧水的用量、染液初始pH、染液初始濃度、溶液中陰離子以及催化劑預(yù)處理溫度等外界因素對(duì)催化劑的光催化性能影響,并對(duì)催化劑的催化機(jī)理進(jìn)行研究。主要內(nèi)容包括:1.采用微波法制備了具有不同形貌的磷酸鈷(Co3(PO_4)2·8H_2O)。其中以六亞甲基亞胺(HMTA)為沉淀劑時(shí)磷酸鈷為花球形分級(jí)結(jié)構(gòu)(fCoP),以尿素為沉淀劑時(shí)磷酸鈷為片形結(jié)構(gòu)(pCoP)。fCoP與pCoP具有相似的光學(xué)吸收性質(zhì)。但是fCoP的表面光電壓信號(hào)強(qiáng)度比pCoP大,這與其花球形結(jié)構(gòu)有關(guān),相互交叉的片結(jié)構(gòu)使光在花球內(nèi)部進(jìn)行多次反射和折射,從而提高光的利用率,進(jìn)一步提高其光電壓信號(hào)強(qiáng)度。fCoP是基于Ostwald熟化機(jī)理形成的,HMTA的存在是fCoP形成的必要條件。采用光助類Fenton反應(yīng),通過降解羅丹明B(RhB)研究了fCoP的光催化性能。內(nèi)部因素研究表明fCoP的催化性能優(yōu)于pCoP。外部因素研究表明RhB溶液的脫色率受fCoP和H_2O2用量的影響,提高RhB溶液的濃度和在降解過程中加入無(wú)機(jī)陰離子會(huì)降低RhB的脫色率。RhB溶液初始pH對(duì)fCoP的催化活性影響小,而對(duì)催化劑進(jìn)行高溫煅燒會(huì)降低催化劑的催化活性。此外,fCoP的催化穩(wěn)定性及結(jié)構(gòu)穩(wěn)定性良好,具有可重復(fù)利用性。對(duì)fCoP光催化降解染料機(jī)理的研究發(fā)現(xiàn)fCoP-Fenton體系的光催化活性是催化氧化與光催化協(xié)同作用的結(jié)果,fCoP分子中的Co2+和PO43-是fCoP高催化活性的主要原因。2.采用微波法制備了具有不同形貌的羥基磷酸銅(Cu_2(OH)PO_4)。通過改變表面活性劑的種類和反應(yīng)濃度,Cu_2(OH)PO_4表現(xiàn)出海膽狀、米粒狀和棱柱體等完全不同的形貌。與傳統(tǒng)水熱法相比,使用磷酸鹽代替磷酸,并將銅磷摩爾比控制在化學(xué)計(jì)量比,大大提高了原料的利用率,減少了磷的排放;同時(shí)將反應(yīng)時(shí)間由3天縮短為30 min,降低了對(duì)能量的消耗;使用尿素代替乙二胺,減少了對(duì)人體和環(huán)境的毒害,是一種環(huán)境友好的合成方法。采用光助類Fenton反應(yīng),通過降解亞甲基藍(lán)(MB)研究了Cu_2(OH)PO_4的光催化性能。內(nèi)部因素研究表明米粒狀Cu_2(OH)PO_4的光催化性能優(yōu)于海膽狀及棱柱狀Cu_2(OH)PO_4。外部因素研究表明MB溶液的脫色率受Cu_2(OH)PO_4和H_2O2用量的影響,提高M(jìn)B溶液的初始濃度會(huì)降低其脫色率。在降解過程中加入無(wú)機(jī)陰離子和改變MB溶液初始pH對(duì)Cu_2(OH)PO_4的催化活性影響小。此外,Cu_2(OH)PO_4的催化穩(wěn)定性及結(jié)構(gòu)穩(wěn)定性良好,具有可重復(fù)利用性。對(duì)Cu_2(OH)PO_4光催化降解染料機(jī)理的研究發(fā)現(xiàn)Cu_2(OH)PO_4-Fenton的光催化活性是催化氧化與光催化協(xié)同作用的結(jié)果,Cu_2(OH)PO_4分子中的Cu_2+-OH是Cu_2(OH)PO_4高催化活性的主要原因。3.采用微波法制備了類線團(tuán)狀結(jié)構(gòu)的磷酸鋯鈷(CoZr(PO_4)2·4H_2O,CZP)。適宜用量的氟化銨和磷酸二氫鈉是得到結(jié)晶性能良好、線團(tuán)結(jié)構(gòu)規(guī)則的磷酸鋯鈷的關(guān)鍵。Zr~(4+)濃度對(duì)磷酸鋯鈷的結(jié)構(gòu)和形貌也有很大的影響,增大Zr~(4+)的濃度使線團(tuán)粒徑增大并且結(jié)構(gòu)變得疏松。研究發(fā)現(xiàn)線團(tuán)狀CZP是基于Ostwald熟化機(jī)理形成的,Co2+的存在是使磷酸鋯由二維六角片形轉(zhuǎn)變?yōu)槿S線團(tuán)狀磷酸鋯鈷的原因。通過降解MB研究了磷酸鋯鈷的光催化性能,結(jié)果表明磷酸鋯鈷為紫外光光催化劑,催化性能穩(wěn)定,具有可重復(fù)利用性。對(duì)磷酸鋯鈷光催化機(jī)理的研究表明HO·是其光催化降解反應(yīng)中的主要活性物種。磷酸鋯鈷還具有一定的吸波性能,對(duì)磷酸鋯鈷的磁導(dǎo)率及其介電常數(shù)進(jìn)行分析,發(fā)現(xiàn)磷酸鋯鈷類材料在高頻波段具有較高的介電損耗和磁損耗,理論上在高頻波段具有良好的吸波性能。但事實(shí)上其吸波能力有限,較差的阻抗匹配特性是造成樣品表現(xiàn)出有限反射損耗的主要原因。
[Abstract]:This paper mainly through the microwave assisted heating method in low temperature and low pressure under the condition of preparation of three kinds of metal phosphate materials, including cobalt phosphate, copper hydroxyphosphate zirconium phosphate and cobalt, and through XRD, SEM, TEM, FT-IR, Raman, TG, DRS and SPV means of material phase, morphology, thermal stability and the optical properties were studied. The three kinds of phosphate as a heterogeneous catalyst used in dyeing wastewater treatment, study the morphology and preparation conditions and internal factors such as catalyst and hydrogen peroxide, dye initial pH, the initial concentration of dye solution, solution from external factors and bardo catalyst pretreatment temperature on Photocatalytic Performance of catalyst the effect and Research on catalytic mechanism of catalyst. The main contents include: 1. by microwave method of cobalt phosphate with different morphologies were prepared by (Co3 (PO_4) 2 - 8H_2O). The six methylene imine (HMTA) as precipitating agent When the flower for the hierarchical structure of spherical cobalt phosphate (fCoP), using urea as precipitating agent for cobalt phosphate sheet structure of (pCoP).FCoP and pCoP have similar optical absorption properties. But the surface photovoltage signal of fCoP is greater than pCoP, which instead of spherical structure, structure of cross the light multiple reflection and refraction in the curd, so as to improve the utilization rate of the light, is formed based on the Ostwald ripening mechanism to further improve the light intensity of.FCoP voltage signal, HMTA is a necessary condition for the formation of fCoP. The photo Fenton like reaction, through the degradation of rhodamine B (RhB) on the photocatalytic performance of fCoP. Study on the internal factors that study on the catalytic performance of pCoP. is better than external factors in fCoP show that the decolorization of RhB solution was affected by fCoP and the content of H_2O2, increase the concentration of RhB solution and adding inorganic anions will decrease in the degradation process of RhB The decolorization rate of.RhB solution initial pH affected the catalytic activity of fCoP is small, and high temperature calcining will decrease the photocatalytic activity of the catalyst. In addition, the catalytic stability and structural stability of fCoP has good reusability. To study the mechanism of photocatalytic degradation of fCoP dye found that the photocatalytic activity of fCoP-Fenton system is catalytic oxidation and the photocatalytic synergy results in the molecule of fCoP Co2+ and PO43-.2. fCoP is the main reason of high catalytic activity by microwave method of copper hydroxyphosphate with different morphologies were prepared by (Cu_2 (OH) PO_4). By changing the type and concentration of surfactant, Cu_2 (OH) PO_4 expression of sea urchin. The morphology of rice shaped prism and completely different. Compared with the traditional hydrothermal method, using phosphate instead of phosphoric acid, and the molar ratio of copper phosphorus control in the stoichiometric ratio, greatly improve the utilization rate of raw materials, reduce The phosphorus emission; while the reaction time is shortened from 3 days to 30 min, reduces the energy consumption; using urea instead of ethylenediamine, reducing the toxicity to human body and environment, is an environmentally friendly synthesis method. The photo Fenton like reaction, through the degradation of methylene blue (MB) of Cu_2 (OH) the photocatalytic properties of PO_4. The research of internal factors showed that the rice like Cu_2 (OH) PO_4 photocatalytic performance is better than that of urchinlike and prismatic Cu_2 (OH) of PO_4. external factors showed that the decoloration efficiency of MB solution by Cu_2 (OH) PO_4 and H_2O2 dosage, initial concentration of MB solution will improve reduce the decolorization rate. The addition of inorganic anions and MB solution initial pH on Cu_2 in the process of degradation (OH) influence the catalytic activity of PO_4. In addition, Cu_2 (OH) catalytic stability and structural stability of PO_4 has good reusability. The Cu_2 (OH) PO_4 photocatalytic degradation of dye Study on the mechanism of the material Cu_2 (OH) PO_4-Fenton photocatalytic activity and photocatalytic oxidation is the result of synergy of Cu_2 (OH) PO_4 in Cu_2+-OH molecule is Cu_2 (OH.3. PO_4) mainly due to high catalytic activity by microwave method zirconium phosphate cobalt type coil like structure were synthesized (CoZr (PO_4 2) 4H_2O, CZP). The suitable amount of ammonium fluoride and sodium dihydrogen phosphate has good crystallization performance, the key.Zr~ zirconium phosphate cobalt coil structure of the rules (4+) concentration of the morphology and structure of zirconium phosphate cobalt also has great influence on the increase of Zr~ (4+) concentration of the aggregate size increases and the structure line loose. The study found that the coil like CZP is formed based on the Ostwald ripening mechanism, Co2+ is made of zirconium phosphate from 2D six angle sheet into three-dimensional coil like zirconium phosphate cobalt. The photocatalytic properties of cobalt zirconium phosphate were investigated by the degradation of MB, results show that phosphorus Zirconium cobalt UV light catalyst, catalytic performance and stability, which can be reused. The research on the photocatalytic mechanism of zirconium phosphate cobalt indicates that HO is the main active species in the photocatalytic degradation reaction. Cobalt zirconium phosphate has the absorbing properties of the zirconium phosphate cobalt permeability and dielectric constant analysis found that zirconium phosphate cobalt material has higher in high-frequency dielectric loss and magnetic loss theory in the high frequency band with good microwave absorbing properties. But in fact, the absorbing capacity is limited, poor impedance matching characteristic is caused by the sample shows the main reasons for the limited reflection loss.

【學(xué)位授予單位】：東華大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36

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