本文選題：Cu + 納米粒子��； 參考：《江西師范大學(xué)》2017年碩士論文

【摘要】：在過去的幾十年里,氫氣被認(rèn)為是一種極具前景的能源載體。然而,尋找安全、高效的方法來儲(chǔ)存和運(yùn)輸氫氣,以轉(zhuǎn)型到氫能社會(huì),依舊面臨巨大的挑戰(zhàn)。氨硼烷由于無毒,擁有高的儲(chǔ)氫質(zhì)量分?jǐn)?shù)(19.6 wt%)和穩(wěn)定性,被認(rèn)為是一種很有前景的化學(xué)儲(chǔ)氫材料。1摩爾氨硼烷在合適的催化劑存在下可以水解產(chǎn)生3摩爾的氫氣。貴金屬催化劑由于具有較高的催化活性,被廣泛用于氨硼烷水解產(chǎn)氫反應(yīng)中,但其價(jià)格昂貴,儲(chǔ)量有限,限制了其廣泛的應(yīng)用。因此,尋找低成本、高活性的非貴金屬催化劑成為了研究熱點(diǎn)。本文圍繞Cu基非貴金屬催化劑的制備、表征以及催化性能開展研究。主要內(nèi)容如下:采用簡(jiǎn)單的方法快速合成了無表面活性劑和載體修飾的非貴金屬M(fèi)o、W、Cr增強(qiáng)Cu催化劑。與Cu納米粒子(15.6 nm)相比,摻雜Mo、W、Cr可以顯著降低納米粒子的顆粒尺寸(5-7 nm)和提高催化劑的分散度。此外,研究結(jié)果表明,摻雜Mo、W、Cr可以降低Cu納米粒子的結(jié)晶度,這些可能導(dǎo)致催化劑擁有較高的催化活性。單獨(dú)的Cu催化劑的催化活性很低,210分鐘才使得氨硼烷水解產(chǎn)生2.6摩爾比的氫氣,單獨(dú)的Mo、W和Cr對(duì)氨硼烷水解產(chǎn)氫反應(yīng)沒有催化活性,而少量Mo、W、Cr摻雜Cu催化劑后(Cu0.9Mo0.1、Cu0.9W0.1和Cu0.95Cr0.05),催化活性得到顯著提高,其中Cu0.9Mo0.1催化劑表現(xiàn)出最優(yōu)的催化性能,可以在3.4分鐘內(nèi)使得氨硼烷完全水解產(chǎn)氫,氫氣轉(zhuǎn)化頻率(TOF)達(dá)到14.9 mol(H2)·mol(metal)-1·min-1,在所有已報(bào)道的Cu催化劑中處于一個(gè)相對(duì)高的值。在室溫下通過簡(jiǎn)單的共還原法合成了非貴金屬M(fèi)o增強(qiáng)CuCo催化劑。與相應(yīng)的單金屬和雙金屬催化劑相比,Cu0.72Co0.18Mo0.1催化劑表現(xiàn)出更高的催化活性,催化氨硼烷水解產(chǎn)氫反應(yīng)的轉(zhuǎn)化頻率為46 mol(H2)·mol(metal)-1·min-1。研究結(jié)果表明,Mo的引入不僅可以減小納米粒子的顆粒尺寸,還可以改變催化劑表面的電子結(jié)構(gòu)。此外,發(fā)現(xiàn)堿的加入會(huì)顯著促進(jìn)氨硼烷水解產(chǎn)氫,而氨硼烷可以穩(wěn)定的存在于堿溶液中,說明堿在氨硼烷水解產(chǎn)氫反應(yīng)中只是起到助催化劑的作用。Cu0.72Co0.18Mo0.1催化劑在加入NaOH(1 M)的情況下,催化氨硼烷完全水解產(chǎn)氫只需約0.6分鐘,氫氣轉(zhuǎn)化頻率達(dá)到119 mol(H2)·mol(metal)-1·min-1,不僅高于所有已報(bào)道的非貴金屬催化劑,而且還高于商業(yè)化的Pt/C催化劑。因此,堿促進(jìn)Cu0.72Co0.18Mo0.1催化劑可以代替貴金屬催化劑用于氨硼烷水解產(chǎn)氫反應(yīng),有望促進(jìn)氨硼烷作為儲(chǔ)氫材料走向?qū)嶋H應(yīng)用。
[Abstract]:In the past few decades, hydrogen has been regarded as a promising energy carrier. However, the challenge of finding safe and efficient ways to store and transport hydrogen to a hydrogen society remains enormous. Because of its nontoxicity, high hydrogen storage mass fraction (19.6 wtt) and stability, aminoborane is considered as a promising chemical hydrogen storage material, which can hydrolyze to produce 3 moles of hydrogen in the presence of suitable catalyst. Due to its high catalytic activity, noble metal catalysts are widely used in the hydrolysis of ammonioborane to produce hydrogen. However, their high price and limited reserves limit their wide application. Therefore, the search for low-cost, high-activity non-precious metal catalysts has become a research hotspot. The preparation, characterization and catalytic properties of Cu-based non-noble metal catalysts were studied in this paper. The main contents are as follows: a simple method was used to rapidly synthesize non-surfactant and carrier modified non-noble metal Mohln / Cr reinforced Cu catalyst. Compared with Cu nanoparticles (15.6 nm), the doping of Mo-WN Cr can significantly reduce the particle size of the nanoparticles and increase the dispersion of the catalyst. In addition, the results show that the crystallinity of Cu nanoparticles can be reduced by doping Mo-WN Cr, which may lead to higher catalytic activity of the catalysts. The catalytic activity of the single Cu catalyst was very low for 210 minutes, which resulted in the hydrolysis of aminoborane to produce 2.6 molar ratio of hydrogen, while the single MohlW and Cr had no catalytic activity for the hydrolysis of ammonioborane to produce hydrogen. However, the catalytic activity of Cu _ (0.9) Mo _ (0.1) Cu _ (0.9) W _ (0.1) and Cu _ (0.95Cr) _ (0.05) C _ (2) was significantly increased after a small amount of Mo _ (Mo) W ~ (+) Cr was doped with Cu catalyst. Among them, the Cu0.9Mo0.1 catalyst showed the best catalytic activity, which could make the ammonia borane completely hydrolyze to produce hydrogen within 3.4 minutes. The conversion frequency of hydrogen is 14.9 mol / h _ 2) mol(metal)-1 min-1, which is a relatively high value in all reported Cu catalysts. The non noble metal Mo reinforced CuCo catalyst was synthesized by a simple co reduction method at room temperature. Compared with the corresponding monometallic and bimetallic catalysts, Cu0.72Co0.18Mo0.1 catalyst showed higher catalytic activity, and the conversion frequency of the hydrogen-producing reaction of ammonioborane hydrolysis was 46 mol / h _ 2) mol(metal)-1 min-1. The results show that the introduction of Mo can not only reduce the particle size of the nanoparticles, but also change the electronic structure of the catalyst surface. In addition, it was found that the addition of alkaloids could significantly promote the hydrolysis of aminoborane to produce hydrogen, and that ammonioborane could exist stably in alkali solution. The results show that alkali can only act as a catalyst in the hydrolysis of ammonioborane to produce hydrogen. Cu0.72Co0.18Mo0.1 catalyst can only be used as catalyst for the complete hydrolysis of ammonioborane to produce hydrogen by adding NaOH(1 M, and it only takes about 0.6 minutes for the complete hydrolysis of aminoborane to produce hydrogen. The hydrogen conversion frequency reached 119mol / h _ 2) mol(metal)-1 min-1, which was higher than that of all reported non-noble metal catalysts, but also higher than commercial Pt/C catalysts. Therefore, the alkali-promoted Cu0.72Co0.18Mo0.1 catalyst can be used in the hydrolysis of ammonioborane to produce hydrogen instead of the noble metal catalyst, which is expected to promote the practical application of aminoborane as a hydrogen storage material.
【學(xué)位授予單位】：江西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;TB383.1

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本文編號(hào)：1830943