發(fā)布時(shí)間：2018-01-08 02:00

  本文關(guān)鍵詞：硼烷氨和氨類(lèi)儲(chǔ)氫材料釋氫反應(yīng)的理論研究　出處：《河南大學(xué)》2015年碩士論文　論文類(lèi)型：學(xué)位論文

  更多相關(guān)文章： 釋氫反應(yīng) 催化 反應(yīng)機(jī)理 從頭算

【摘要】：氫能作為一種高能量密度、清潔、可再生的綠色新能源,引起了世界各國(guó)的高度關(guān)注。目前,儲(chǔ)氫問(wèn)題是氫能應(yīng)用的主要瓶頸。確定材料的釋氫機(jī)理是改進(jìn)儲(chǔ)氫材料性能和開(kāi)發(fā)新型儲(chǔ)氫材料的關(guān)鍵因素。本文研究了當(dāng)前比較熱門(mén)的硼烷氨和氨類(lèi)潛在儲(chǔ)氫材料的釋氫反應(yīng)機(jī)理,旨在從理論上確定單分子儲(chǔ)氫材料難于釋氫的原因,并為其尋找有效的催化劑,從而為開(kāi)發(fā)高效、清潔和可行的儲(chǔ)氫材料提供理論依據(jù)。共開(kāi)展了以下三個(gè)方面的研究：1.采用分子軌道理論探究了鋁烷膦和硼烷膦在有無(wú)硼烷或鋁烷催化下的釋氫反應(yīng)機(jī)理。首先在MP2/aug-cc-pVDZ水平下優(yōu)化了所有駐點(diǎn)的構(gòu)型,然后在CCSD(T)/aug-cc-pVTZ水平下對(duì)MP2優(yōu)化的幾何構(gòu)型進(jìn)行了能量校正。理論結(jié)果表明,單分子的鋁烷膦和硼烷膦,釋氫能壘高于Al-P/B-P鍵的離解能,釋氫反應(yīng)無(wú)法進(jìn)行。催化劑鋁烷和硼烷都可以促進(jìn)鋁烷膦的釋氫反應(yīng),但是當(dāng)對(duì)應(yīng)的前期絡(luò)合物穩(wěn)定存在時(shí),硼烷膦的釋氫能壘仍然高于A1-P離解能,釋氫過(guò)程難以進(jìn)行。同樣,對(duì)于硼烷膦的釋氫過(guò)程,鋁烷和硼烷也可以大幅降低釋氫能壘,有一定的催化作用,并且通過(guò)比較得知,硼烷的催化效果優(yōu)于鋁烷。除此之外,在鋁烷和烷催化下,硼烷膦比鋁烷膦更有可能成為潛在的儲(chǔ)氫材料。因此,對(duì)于膦系列的儲(chǔ)氫材料,由于它們的釋氫能壘高于Al-P/B-P鍵的離解能,需要為其尋找有效的催化劑以降低釋氫能壘。硼烷將是較合適的催化劑,在它的催化下,硼烷膦釋氫反應(yīng)的能壘低于B-P鍵的斷裂能,釋氫過(guò)程容易進(jìn)行。2.采用量子化學(xué)方法研究了甲胺在有無(wú)硼烷、鋁烷、乙硼烷、乙鋁烷和硼烷-鋁烷催化下的釋氫反應(yīng)機(jī)理。首先在MP2/aug-cc-pVDZ水平下優(yōu)化了所有駐點(diǎn)的構(gòu)型,然后基于此優(yōu)化的幾何構(gòu)型,在CCSD(T)/aug-cc-pVTZ水平下進(jìn)行了能量校正。結(jié)果表明,單分子甲胺釋氫能壘較高,釋氫反應(yīng)難以進(jìn)行,因此釋氫過(guò)程需要合適的催化劑。所研究的催化劑都可以加快甲胺的釋氫反應(yīng),然而,對(duì)于單分子催化劑硼烷和鋁烷來(lái)說(shuō),由于它們催化下的甲胺釋氫能壘仍然高于其對(duì)應(yīng)前期絡(luò)合物中的B-N/Al-N鍵的離解能,因此并無(wú)真正的催化作用。而雙分子催化劑乙硼烷、乙鋁烷和混合催化劑硼烷-鋁烷可以大幅降低甲胺的釋氫能壘,有較好的催化作用,且混合催化劑硼烷-鋁烷由于催化釋氫反應(yīng)能壘最低和反應(yīng)歷程最短,因此它的催化效果最好。此外,通過(guò)比較各個(gè)催化劑的相同點(diǎn)和不同點(diǎn),得知?dú)滏I的形成和六元環(huán)結(jié)構(gòu)是降低釋氫能壘的兩個(gè)重要因素。3.在CCSD(T)/aVTZ//MP2/aVDZ水平下研究了硼氫化合物和鋁氫化合物催化甲基肼釋氫反應(yīng)的反應(yīng)機(jī)理。結(jié)果表明,單分子的甲基肼釋氫能壘太高,釋氫反應(yīng)難以進(jìn)行。而所研究的五種催化劑既可以進(jìn)攻甲基肼氨基中的N原子,也可以進(jìn)攻亞氨基中的N原子,并且都可以加快甲基肼的釋氫反應(yīng)。對(duì)于單分子的硼烷和鋁烷,當(dāng)對(duì)應(yīng)的前期絡(luò)合物穩(wěn)定存在時(shí),其催化甲基肼釋氫反應(yīng)的能壘仍然較高,并無(wú)真正的催化作用；而雙分子催化劑可以使甲基肼有效的釋氫,且混合催化劑硼烷-鋁烷的催化效果最好。此外,經(jīng)過(guò)比較得知,雖然催化劑更容易進(jìn)攻甲基肼亞氨基的N原子,但其釋氫能壘高于催化劑進(jìn)攻氨基N原子的能壘,因此,當(dāng)催化劑進(jìn)攻甲基肼的氨基N原子時(shí),釋氫反應(yīng)更容易進(jìn)行。
[Abstract]:Hydrogen is a kind of high energy density, clean, new green renewable energy, has aroused great attention in the world. At present, hydrogen storage is the main bottleneck of the application of hydrogen energy. Determining the material release mechanism of hydrogen is the key factor to improve the performance of hydrogen storage materials and development of new hydrogen storage materials. Hydrogen reaction mechanism was studied in this paper. Release the current hot ammonia borane ammonia and potential hydrogen storage materials, to ascertain the cause of single molecular hydrogen storage material is difficult to release hydrogen from the theory, and to find effective catalyst for the development of efficient, so as to provide a theoretical basis for the hydrogen storage materials, clean and feasible. A total of three studies were carried out 1.: using molecular orbital theory to explore the aluminum alkyl phosphine and phosphine borane in a borane or alanes catalyzed hydrogen release reaction mechanism. First optimized at the MP2/aug-cc-pVDZ level all of the stationary points of the configuration, and then in the CCSD (T) /aug-cc-pVTZ levels on the geometry optimization of MP2 of energy correction. The theoretical results show that the single molecule aluminum alkyl phosphine and phosphine borane, release hydrogen dissociation barrier is higher than that of the Al-P/B-P bond can release hydrogen reaction. The catalyst cannot alanes and borane can promote hydrogen release of aluminum alkyl phosphine, but when there is a stable complex corresponding to the early release of phosphine borane, hydrogen barrier is still higher than the A1-P dissociation energy, hydrogen release process is very difficult. Similarly, the process of hydrogen release phosphine borane, aluminum alkyl borane and also can significantly reduce the release of hydrogen barrier has a catalytic effect, and the result shows that the catalytic effect of borane better than the alanes. In addition, the aluminum alkyl and alkyl phosphine borane catalyzed alkyl phosphine than aluminum is more likely to be a potential hydrogen storage materials. Therefore, the hydrogen storage materials for phosphine series, due to their higher hydrogen dissociation barrier release Al-P/ B-P key can be. For which you want to find effective catalyst to reduce the release of hydrogen barrier. Borane will be a catalyst for more suitable, in its catalyzed borane hydrogen release reaction of phosphine fracture energy barrier than the B-P bond energy, hydrogen release process easy to.2. studied there in the methylamine borane, using quantum chemical method of aluminum alkoxide. B borane hydrogen release reaction mechanism of ethylene alanes and borane catalyzed alanes. First optimized at the MP2/aug-cc-pVDZ level of all point configuration, then the geometry optimization based on CCSD (T) /aug-cc-pVTZ level of energy correction. The results show that the single molecule hydrogen barrier of methylamine release higher hydrogen release the reaction is difficult, so the hydrogen release process requires a suitable catalyst. The catalyst can accelerate the reaction of hydrogen release, methylamine however, for single molecule catalyst borane and aluminium alkyl, because they are under the catalysis of methylamine release hydrogen barrier is still high In the early B-N/Al-N bond dissociation in the complex, so there is no real catalysis. And bimolecular catalyst diborane, ethylene alanes and mixed catalyst borane alanes can greatly reduce the hydrogen barrier release of methylamine, have good catalytic effect, and the mixed catalyst borane alanes due to catalytic hydrogen release reaction the lowest energy barrier and the reaction mechanism is the shortest, so it's the best catalytic effect. In addition, through the comparison of different catalysts and different points, that the formation of hydrogen bonds and six membered ring structure is the two important factors to reduce.3. release hydrogen barrier in CCSD (T) level on the reaction mechanism of /aVTZ//MP2/aVDZ boron hydrogen compounds hydrogen and aluminum compounds catalyzed by methyl hydrazine hydrogen release reaction. The results show that the single molecule of methyl hydrazine release hydrogen barrier is too high, difficult to release hydrogen. Five kinds of catalysts and the study can attack amino methyl hydrazine The N atoms, can also attack the imino atoms in the N, and can accelerate the reaction of methyl hydrazine hydrogen. For single molecule borane and aluminium alkyl, when there are early stable complex corresponding, the catalytic reaction of methyl hydrazine hydrogen energy barrier is still high, there is no real catalytic effect; while the two catalysts can make methyl hydrazine hydrogen effectively, and the catalytic effect of mixed catalyst borane alanes best. In addition, it was found that although the catalyst is easier to attack the imino methyl hydrazine N atoms, but the release of hydrogen barrier was higher than offensive amino N atomic energy barrier, therefore, when the catalyst the attack of methyl hydrazine amino N atoms, hydrogen release reaction more easily.

【學(xué)位授予單位】：河南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TB34;TQ116.2

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