催化反应制备碳化硅纳米粉体的密度泛函理论计算及实验研究

doi:10.7503/cjcu20170259

摘要/Abstract

摘要：

以Si₅₅, Si₄₃M₁₂和Si₃₇M₁₈(M=Fe, Co或Ni)团簇为模型, 采用密度泛函理论(DFT)研究了Fe, Co及Ni纳米团簇催化硅粉转化为SiC的机理. 计算结果表明, Fe, Co及Ni纳米催化剂先与Si形成合金, 拉长并弱化Si—Si键的强度, 起到活化Si粉的作用; 合金的形成有利于C原子的吸附及Si原子和C原子间的反应; Fe的催化能力强于Co和Ni. 在此基础上, 以Si粉和酚醛树脂为原料, 以Fe, Co及Ni硝酸盐为催化剂前驱体, 通过微波加热反应制备了3C-SiC纳米粉体. 研究了催化剂种类、反应温度、催化剂用量和反应时间等对制备3C-SiC纳米粉体的影响. 结果表明, 催化剂Fe, Co和Ni的加入均可显著降低3C-SiC的合成温度. 当以2.0%(质量分数)的Fe为催化剂时, Si粉在1100 ℃下反应30 min后即可全部转化为3C-SiC纳米粉体; 而在相同条件下, 无催化剂时Si粉的完全转化温度为1250 ℃; Fe的催化效果优于Co和Ni, 与DFT计算结果吻合.

关键词: 密度泛函理论, 碳化硅纳米粉体, 催化碳化反应, 硅粉, 酚醛树脂

Abstract:

Taking Si₅₅, Si₄₃M₁₂ and Si₃₇M₁₈(M=Fe, Co or Ni) cluster as models, density functional theory(DFT) was used to investigate the catalytic mechanism of Fe, Co and Ni catalysts on the formation of SiC using Si and C as starting materials. The results show that Fe, Co and Ni nano catalysts will form alloy with Si first, and then elongate the bond length of Si—Si and weaken its bond strength, finally activate Si powder. The formation of alloy is favorable to the adsorption of C atom, and then accelerate the reaction process between Si and C atoms. The catalytic performance of Fe is better than Co and Ni. On this basis, 3C-SiC nano powders were synthesized by a microwave reaction method using silicon powders and phenolic resin as raw materials, and ferric/cobalt/nickel nitrate as catalyst precursor. The effects of catalyst type, heat treatment temperature, catalyst content and holding time on the preparation of 3C-SiC were investigated. Results indicated that the addition of Fe, Co and Ni significantly decreased the synthesis temperature of 3C-SiC. Si powder can completely transform into 3C-SiC at 1100 ℃ for 30 min using 2.0% Fe as catalyst. In contrast, for the sample without any catalysts, corresponding temperature was as high as 1250 ℃. Moreover, the experiment results also indicated that the catalytic performance of Fe is better than Co and Ni, which is in consistent with the DFT calculations.

Key words: Density functional theory(DFT), 3C-SiC nano powders, Catalytic carbonization reaction, Silicon powder, Phenolic resin

中图分类号:

O641
TB35

TrendMD:

王军凯, 韩磊, 黄亮, 张海军, 李俊怡, 李赛赛. 催化反应制备碳化硅纳米粉体的密度泛函理论计算及实验研究. 高等学校化学学报, 2017, 38(9): 1602.

WANG Junkai, HAN Lei, HUANG Liang, ZHANG Haijun, LI Junyi, LI Saisai. Density Functional Theory Calculation and Experimental Study of Catalytic Synthesis SiC Nano Powders^†. Chem. J. Chinese Universities, 2017, 38(9): 1602.

图/表 15

Fig.1 Calculation models of Si55(A), Si43M12(B) and Si37M18(C)(M=Fe, Co, Ni) nanoclusters

Table 1 Cohesive energies of Si55, Si43M12 and Si37M18 nanoclusters and adsorption energy of C atom adsorbed on(111) face of Si55, Si43M12 and Si37M18 nanoclusters

Clusters composition	Cohesive energy/(kJ·mol^-1)	Adsorption energy/(kJ·mol^-1)
Si₅₅	582.458
Si₄₃Fe₁₂	1547.250
Si₄₃Co₁₂	1026.045
Si₄₃Ni₁₂	940.142
Si₃₇Fe₁₈	1608.136
Si₃₇Co₁₈	1108.224
Si₃₇Ni₁₈	1165.307
C—Si₅₅		13.6526
C—Si₄₃Fe₁₂		37.2821
C—Si₄₃Co₁₂		15.7530
C—Si₄₃Ni₁₂		19.9538
C—Si₃₇Fe₁₈		36.2319
C—Si₃₇Co₁₈		18.6411
C—Si₃₇Ni₁₈		41.4829

Table 2 Bond length of Si atoms at edge sites on (111) face of Si55, Si43M12 and Si37M18 clusters

Clusters composition	Bond length of Si atoms at edge sites on (111) face/nm	Clusters composition	Bond length of Si atoms at edge sites on (111) face/nm
Si₅₅	0.4619	Si₃₇Fe₁₈	0.5384
Si₄₃Fe₁₂	0.4950	Si₃₇Co₁₈	0.4989
Si₄₃Co₁₂	0.4738	Si₃₇Ni₁₈	0.4990
Si₄₃Ni₁₂	0.4625

Fig.2 Adsorption models between metal nanocluster and C atom, C—Si55(A), C—Si43M12(B) and C—Si37M18(C)

Fig.3 Catalytic mechanism of SiC formation using Fe, Co and Ni nanocluster catalysts

Fig.4 XRD patterns of samples fired at 1100 ℃ for 30 min with 2% different catalysts

Fig.5 Crystalline phase contents of samples fired at 1100 ℃ for 30 min with 2% different kinds of catalysts

Fig.6 XRD patterns of samples fired at various temperatures for 30 min with 2%Fe catalysts Temperature/℃: a. 1000; b. 1050; c. 1100; d. 1150; e. 1200, f. 1250; g. 1300.

Fig.7 Crystalline phase contents of samples fired at various temperatures for 30 min with 2%Fe catalysts a. Si; b. SiC.

Fig.8 XRD patterns of samples fired at 1100 ℃ for various holding time with 2.0%Fe catalysts Temperature/min: a. 10; b. 20; c. 30.

Fig.9 Crystalline phase contents of samples fired at 1100 ℃ for various holding time with 2.0%Fe catalysts a. Si; b. SiC.

Fig.10 XRD patterns of samples fired at 1100 ℃ for 30 min with various contents of Fe catalysts Mass fraction of Fe: a. 0; b. 0.5%; c. 1.0%;d. 1.5%; e. 2.0%.

Fig.11 Crystalline phase contents of samples fired at 1100 ℃ for 30 min with various contents of Fe catalysts a. Si; b. SiC.

Fig.12 SEM images(A) of the as-prepared 3C-SiC(1100 ℃/30 min) with 2.0%Fe as catalyst and EDS results(B) of selected point 1 in Fig.12(A)

Fig.13 TEM(A, B) and HRTEM(C) images of as-prepared 3C-SiC whiskers

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