BCN納米片的制備、復(fù)合及性能研究
發(fā)布時(shí)間：2018-11-15 11:18
【摘要】：新型無(wú)機(jī)非金屬材料硼碳氮(BCN)納米片,由于具有可調(diào)節(jié)的帶隙寬度和良好的穩(wěn)定性等優(yōu)點(diǎn),近年來(lái)引起人們的廣泛關(guān)注。本論文針對(duì)BCN納米片的制備和性能進(jìn)行了系統(tǒng)研究。提出了金屬鈉(Na)插層剝離、置換法和煅燒法等幾種利用固相反應(yīng)制備BCN納米片的方法,并研究了 BCN納米片在稀磁半導(dǎo)體、非線性光學(xué)、超級(jí)電容器和光催化等領(lǐng)域的應(yīng)用,分析了 BCN納米片結(jié)構(gòu)對(duì)性能的影響。具體研究?jī)?nèi)容如下:(1)Na插層剝離制備BCN納米片及其鐵磁性性能研究以金屬Na插層剝離的氮化硼納米片(BNNSs)和石墨烯為原料,將兩者隨機(jī)交疊在一起,然后高溫煅燒處理將石墨烯中的C原子引入BNNSs晶格中,形成BCN納米片。采用這種方法可以高效地制備BCN材料,并通過(guò)控制石墨烯的添加量可以實(shí)現(xiàn)不同C含量的BCN材料的制備。得到的BCN納米片厚度大約3 nm,具有完整的晶格結(jié)構(gòu)。BCN納米片中的C原子附近的電子態(tài)呈現(xiàn)自旋極化的現(xiàn)象,導(dǎo)致BCN納米片具有磁性。相比于抗磁性的石墨烯和BNNSs,BCN納米片表現(xiàn)出明顯的鐵磁性,居里溫度可達(dá)到463 K,是一種常溫鐵磁性半導(dǎo)體材料。另外BCN納米片在磁場(chǎng)中可以實(shí)現(xiàn)定向排列,為下一步BCN材料的實(shí)際應(yīng)用提供了實(shí)驗(yàn)基礎(chǔ)。(2)置換法制備BCN納米片及其非線性光學(xué)性能研究采用Na剝離方法能高效制備BCN納米片,但是實(shí)驗(yàn)過(guò)程較復(fù)雜,我們采用球磨的方法代替Na剝離過(guò)程,研究了置換法制備BCN納米片的新方法。置換法制備的BCN納米片具有良好的晶格結(jié)構(gòu)和極薄的片層厚度(3 nm)。BCN納米片表現(xiàn)出非常強(qiáng)的非線性吸收性能。BCN納米片在較低能量密度下,表現(xiàn)出顯著的可飽和吸收特性,而在高能量密度下表現(xiàn)出反飽和吸收的特性。通過(guò)控制納米片中C含量的大小可以實(shí)現(xiàn)對(duì)BCN納米片的非線性性能調(diào)控。研究結(jié)果表明BCN納米片可以作為一種新型的非線性光學(xué)材料,具有很大的應(yīng)用前景。(3)固相合成制備BCN納米片及其超電性能研究采用Na剝離和置換法得到BCN納米片中C含量整體較少。為了進(jìn)一步提高BCN納米片中的碳含量,我們提出直接煅燒C源、B源和N源的固相合成方法制備BCN納米片。研究結(jié)果發(fā)現(xiàn)利用這種方法可以制備得到C含量高達(dá)60 at%以上的多孔BCN納米片。多孔BCN納米片的厚度大約在1.7 nm左右,具有較好的晶格結(jié)構(gòu)。多孔BCN納米片具有良好的導(dǎo)電性能和較大的比表面積。因此這種多孔BCN納米片可以利用其優(yōu)秀的電學(xué)性能應(yīng)用在超級(jí)電容器領(lǐng)域。實(shí)驗(yàn)結(jié)果發(fā)現(xiàn),BCN納米片作為工作電極,具有良好的電容性能。在0.1A/g的電流密度下BCN納米片的容量為407 F/g,說(shuō)明BCN納米片作為工作電極具有非常高的容量。研究結(jié)果表明BCN納米片作為一種新型的超電材料,具有很大的應(yīng)用前景。(4)BCN納米片、0D/2D CdS/BCN和0D/2D CdS/MoS2復(fù)合材料的光催化性能研究C原子的引入能夠明顯的降低BCN材料的帶隙,通過(guò)XPS、莫特-肖特基曲線和紫外-可見(jiàn)吸收漫反射測(cè)試,不僅發(fā)現(xiàn)隨著C含量的增加BCN納米片的帶隙逐漸降低,還發(fā)現(xiàn)BCN納米片的能級(jí)結(jié)構(gòu)與水的帶隙相匹配。通過(guò)BCN納米片的光催化降解染料和光催化產(chǎn)氫性能測(cè)試,發(fā)現(xiàn)BCN納米片可以作為一種新型光催化材料應(yīng)用于能源與環(huán)境領(lǐng)域。以0.5 wt%的Pt做助催化劑,BCN納米片在全光下產(chǎn)氫效率可以達(dá)到400 μmol h-1g-1。BCN納米片除了自身具有一定的光催化產(chǎn)氫性質(zhì)以外,它還可以與其它傳統(tǒng)光催化劑進(jìn)行復(fù)合,提高其光產(chǎn)氫性能。以0D/2D CdS/BCN納米復(fù)合物為研究對(duì)象,發(fā)現(xiàn)該復(fù)合物的光產(chǎn)氫效率可以達(dá)到2.39 mmol h-1 g-1,遠(yuǎn)高于單純的CdS和BCN納米片的光產(chǎn)氫效率。但是發(fā)現(xiàn),雖然CdS納米顆�？梢苑植荚贐CN納米片表面,但是兩者之間的電子傳導(dǎo)存在一定的阻礙,這不利于光催化產(chǎn)氫性能的提高。為了克服這個(gè)障礙,設(shè)計(jì)采用二維過(guò)渡金屬硫化物代替BCN納米片作為基底,制備了 0D/2D CdS/MoS2納米復(fù)合物,其光產(chǎn)氫效率可以達(dá)到35.6 mmol h-1 g-1,而且該復(fù)合物結(jié)構(gòu)可以有效抑制CdS催化劑的硫腐蝕,具有非常高的光產(chǎn)氫循環(huán)穩(wěn)定性。
[Abstract]:The new inorganic non-metallic material boron-carbon-nitrogen (BCN) nanosheet has attracted wide attention in recent years due to the advantages of adjustable band gap width and good stability. The preparation and properties of the BCN nano-sheet are systematically studied. The method of preparing BCN nanosheet by solid phase reaction, such as metal sodium (Na) insertion layer stripping, displacement method, and sintering method, is put forward, and the application of the BCN nano-sheet in the fields of dilute magnetic semiconductor, non-linear optics, super capacitor and photocatalysis is also studied. The effect of the structure of the BCN on the performance is analyzed. The specific research contents are as follows: (1) the preparation of the BCN nano-sheet and the ferromagnetic properties of the Na plug-in layer are carried out, and the boron nitride nano-sheets (BNSPs) and the graphene which are separated by the metal Na-inserting layer are used as raw materials, and the two are randomly overlapped together, and then the C atoms in the graphene are introduced into the BNNS crystal lattice by the high-temperature sintering treatment to form the BCN nano-sheet. The BCN material can be prepared with high efficiency by adopting the method, and the preparation of the BCN material with different C content can be realized by controlling the addition amount of the graphene. The resulting BCN nanosheet has a thickness of about 3 nm and has a complete lattice structure. The electron state near the C atom in the BCN nanosheet exhibits spin-polarization, resulting in a magnetic property of the BCN nanosheet. Compared with the anti-magnetic graphene and the BNNS, the BCN nano-sheet shows obvious ferromagnetic property, and the Curie temperature can reach 463K, and is a normal-temperature ferromagnetic semiconductor material. in addition, that BCN nano-sheet can realize the directional arrangement in the magnetic field, and provides an experimental basis for the practical application of the next BCN material. (2) The preparation of the BCN nanosheet and its non-linear optical properties by the displacement method can be used to prepare the BCN nano-sheet with high efficiency, but the experimental process is more complicated. We use the method of ball-milling instead of the Na-stripping process, and the new method for preparing the BCN nano-sheet by the displacement method is studied. The BCN nanosheet prepared by the displacement method has a good lattice structure and a very thin layer thickness (3 nm). the bcn nanosheets exhibit very strong non-linear absorption properties. The BCN nanosheets exhibit significant saturable absorption properties at lower energy densities and exhibit anti-saturation absorption at high energy density. The control of the nonlinear properties of the BCN nanosheet can be achieved by controlling the size of the C content in the nanosheet. The results show that the BCN nanosheet can be used as a new nonlinear optical material and has a great application prospect. (3) The preparation of the BCN nano-sheet and its super-electrical property by solid-phase synthesis, the content of C content in the BCN nano-sheet is less than that of the BCN nano-sheet by the method of Na-stripping and displacement. In order to further improve the carbon content in the BCN nano-sheet, the solid-phase synthesis method of the direct-fired C-source, the B-source and the N-source was proposed to prepare the BCN nanosheet. The results show that a porous BCN nanosheet with a C content of up to 60 at% can be prepared by this method. The thickness of the porous BCN nanosheet is about 1. 7 nm, and has a good lattice structure. The porous BCN nanosheet has a good electrical conductivity and a larger specific surface area. Therefore, the porous BCN nano-sheet can be applied to the field of the super capacitor by using the excellent electrical performance. The experimental results show that the BCN nanosheet is used as a working electrode and has good capacitance performance. The capacity of the BCN nanosheet was 407 F/ g at a current density of 0. 1A/ g, indicating that the BCN nanosheet had a very high capacity as the working electrode. The results show that the BCN nanosheet is a new type of super-electric material and has a great application prospect. (4) The photocatalytic performance of the BCN nano-sheet, the 0D/ 2D CdS/ BCN and the 0D/ 2D CdS/ MoS2 composite material can obviously reduce the band gap of the BCN material, and through the XPS, the Mott-Schottky curve and the ultraviolet-visible absorption diffuse reflection test, It is not only found that the band gap of the BCN nanosheet decreases with the increase of C content, but also that the energy level structure of the BCN nano-sheet is matched with the band gap of water. It is found that the BCN nanosheet can be used as a new type of photo-catalytic material in the field of energy and environment. in addition to its own photocatalytic hydrogen-producing property, the BCN nanosheet can be compounded with other conventional photocatalysts to improve its light-producing performance. The light-producing efficiency of the composite was 2.39 mmol/ h-1 g-1, which was much higher than that of the pure CdS and BCN nanoparticles. However, it has been found that, although CdS nanoparticles can be distributed on the surface of the BCN nanosheet, there is a certain barrier between the electron conduction between the two, which is not conducive to the improvement of the photocatalytic hydrogen production performance. In order to overcome this obstacle, a 2D/ 2D CdS/ MoS2 nano-composite was prepared by using a two-dimensional transition metal sulfide instead of the BCN nano-sheet as a substrate. The light-producing efficiency of the composite was 35. 6 mmol/ h-1 g-1, and the composite structure can effectively inhibit the sulfur corrosion of the CdS catalyst. with very high light-producing cycle stability.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O613.81;TB383.1
本文編號(hào)：2333166
[Abstract]:The new inorganic non-metallic material boron-carbon-nitrogen (BCN) nanosheet has attracted wide attention in recent years due to the advantages of adjustable band gap width and good stability. The preparation and properties of the BCN nano-sheet are systematically studied. The method of preparing BCN nanosheet by solid phase reaction, such as metal sodium (Na) insertion layer stripping, displacement method, and sintering method, is put forward, and the application of the BCN nano-sheet in the fields of dilute magnetic semiconductor, non-linear optics, super capacitor and photocatalysis is also studied. The effect of the structure of the BCN on the performance is analyzed. The specific research contents are as follows: (1) the preparation of the BCN nano-sheet and the ferromagnetic properties of the Na plug-in layer are carried out, and the boron nitride nano-sheets (BNSPs) and the graphene which are separated by the metal Na-inserting layer are used as raw materials, and the two are randomly overlapped together, and then the C atoms in the graphene are introduced into the BNNS crystal lattice by the high-temperature sintering treatment to form the BCN nano-sheet. The BCN material can be prepared with high efficiency by adopting the method, and the preparation of the BCN material with different C content can be realized by controlling the addition amount of the graphene. The resulting BCN nanosheet has a thickness of about 3 nm and has a complete lattice structure. The electron state near the C atom in the BCN nanosheet exhibits spin-polarization, resulting in a magnetic property of the BCN nanosheet. Compared with the anti-magnetic graphene and the BNNS, the BCN nano-sheet shows obvious ferromagnetic property, and the Curie temperature can reach 463K, and is a normal-temperature ferromagnetic semiconductor material. in addition, that BCN nano-sheet can realize the directional arrangement in the magnetic field, and provides an experimental basis for the practical application of the next BCN material. (2) The preparation of the BCN nanosheet and its non-linear optical properties by the displacement method can be used to prepare the BCN nano-sheet with high efficiency, but the experimental process is more complicated. We use the method of ball-milling instead of the Na-stripping process, and the new method for preparing the BCN nano-sheet by the displacement method is studied. The BCN nanosheet prepared by the displacement method has a good lattice structure and a very thin layer thickness (3 nm). the bcn nanosheets exhibit very strong non-linear absorption properties. The BCN nanosheets exhibit significant saturable absorption properties at lower energy densities and exhibit anti-saturation absorption at high energy density. The control of the nonlinear properties of the BCN nanosheet can be achieved by controlling the size of the C content in the nanosheet. The results show that the BCN nanosheet can be used as a new nonlinear optical material and has a great application prospect. (3) The preparation of the BCN nano-sheet and its super-electrical property by solid-phase synthesis, the content of C content in the BCN nano-sheet is less than that of the BCN nano-sheet by the method of Na-stripping and displacement. In order to further improve the carbon content in the BCN nano-sheet, the solid-phase synthesis method of the direct-fired C-source, the B-source and the N-source was proposed to prepare the BCN nanosheet. The results show that a porous BCN nanosheet with a C content of up to 60 at% can be prepared by this method. The thickness of the porous BCN nanosheet is about 1. 7 nm, and has a good lattice structure. The porous BCN nanosheet has a good electrical conductivity and a larger specific surface area. Therefore, the porous BCN nano-sheet can be applied to the field of the super capacitor by using the excellent electrical performance. The experimental results show that the BCN nanosheet is used as a working electrode and has good capacitance performance. The capacity of the BCN nanosheet was 407 F/ g at a current density of 0. 1A/ g, indicating that the BCN nanosheet had a very high capacity as the working electrode. The results show that the BCN nanosheet is a new type of super-electric material and has a great application prospect. (4) The photocatalytic performance of the BCN nano-sheet, the 0D/ 2D CdS/ BCN and the 0D/ 2D CdS/ MoS2 composite material can obviously reduce the band gap of the BCN material, and through the XPS, the Mott-Schottky curve and the ultraviolet-visible absorption diffuse reflection test, It is not only found that the band gap of the BCN nanosheet decreases with the increase of C content, but also that the energy level structure of the BCN nano-sheet is matched with the band gap of water. It is found that the BCN nanosheet can be used as a new type of photo-catalytic material in the field of energy and environment. in addition to its own photocatalytic hydrogen-producing property, the BCN nanosheet can be compounded with other conventional photocatalysts to improve its light-producing performance. The light-producing efficiency of the composite was 2.39 mmol/ h-1 g-1, which was much higher than that of the pure CdS and BCN nanoparticles. However, it has been found that, although CdS nanoparticles can be distributed on the surface of the BCN nanosheet, there is a certain barrier between the electron conduction between the two, which is not conducive to the improvement of the photocatalytic hydrogen production performance. In order to overcome this obstacle, a 2D/ 2D CdS/ MoS2 nano-composite was prepared by using a two-dimensional transition metal sulfide instead of the BCN nano-sheet as a substrate. The light-producing efficiency of the composite was 35. 6 mmol/ h-1 g-1, and the composite structure can effectively inhibit the sulfur corrosion of the CdS catalyst. with very high light-producing cycle stability.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O613.81;TB383.1
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 張明文;羅志珊;周敏;黃彩進(jìn);王心晨;;層狀Co/h-BCN納米復(fù)合材料光催化分解水產(chǎn)氧研究（英文）[J];Science China Materials;2015年11期
，本文編號(hào)：2333166
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