复合金属CuCr2O4表面CNCl水解反应机理研究

doi:10.11949/0438-1157.20251122

摘要/Abstract

摘要：

该研究针对高毒性、难水解的氯化氰（CNCl）污染问题，系统探讨了尖晶石型双金属氧化物CuCr₂O₄表面催化CNCl水解的反应机理。基于密度泛函理论（DFT），通过构建（100）、（110）和（111）晶面的完美及氧空位缺陷模型，分析了表面稳定性、吸附特性与水解路径。研究表明，不同晶面结构与氧空位缺陷共同调控了水解路径与反应能垒，其中（110）氧空位表面展现出最优的催化协同性。研究构建了吸附能与反应能的预测模型，揭示了Cu与Cr之间的电子协同与位点互补机制是提升水解效率的关键。该工作为设计高效双金属水解催化剂提供了理论依据，该领域未来研究将侧重于实验验证及模型向其他尖晶石体系的拓展应用。

关键词: 分子模拟, 催化, 计算化学, 水解, 动力学理论

Abstract:

This study systematically investigated the reaction mechanism of the hydrolysis of highly toxic and difficult to hydrolyze cyanogen chloride (CNCl) on the surface of spinel-type bimetallic oxide CuCr₂O₄ catalyst. Based on density functional theory, by constructing perfect and oxygen vacancy defect models of (100), (110) and (111) crystal planes, the surface stability, adsorption characteristics and hydrolysis pathways were analyzed. Research showed that different crystal plane structures and oxygen vacancy defects jointly regulate the hydrolysis path and reaction energy barrier, among which the (110) oxygen vacancy surface exhibits the best catalytic synergy. The study established a predictive model for adsorption energy and reaction energy, revealing that the electronic cooperation and site complementarity between Cu and Cr is the key to enhancing the hydrolysis efficiency. This work provides a theoretical basis for designing efficient bimetallic hydrolysis catalysts. Future research in this field will focus on experimental verification and the expansion of the model to other spinel systems.

Key words: molecular simulation, catalysis, computational chemistry, hydrolysis, kinetic theory

中图分类号:

TQ13

宋振超, 韩嘉豪, 张凌旋, 武越, 李聪明. 复合金属CuCr₂O₄表面CNCl水解反应机理研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251122.

Zhenchao SONG, Jiahao HAN, Lingxuan ZHANG, Yue WU, Congming LI. Study on the hydrolysis reaction mechanism of CNCl on the surface of composite metal CuCr₂O₄[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251122.

图/表 10

表1 复合金属氧化物CuCr2O4不同终端结构的表面与亚表面原子的化学配比以及对应的表面能

Table 1 Chemical composition and surface energy of surface and sub-surface atoms of CuCr2O4 composite metal oxide with different terminal structures

表面	终端结构	表面终端原子	亚表面终端原子	表面能σ (eV·Å^-2)
(100)	T1	Cu*1	Cr2+O4	0.14
(100)	T2	Cr2+O4	Cu*1	0.03
(100)	T3	Cr2+O2	Cu*1	0.10
(100)	T4	O*2	Cu*1	0.28
(110)	T1	Cu2+Cr2+O*4	Cr2+O4	0.15
(110)	T2	Cr2+O4	Cu2+Cr2+O*4	0.07
(110)	T3	Cr2+O2	Cu2+Cr2+O*4	0.09
(110)	T4	O*2	Cu2+Cr2+O*4	0.17
(111)	T1	Cu1+Cr1	Cu1+O4	0.22
(111)	T2	Cu1+Cr1	O*4	0.06
(111)	T3	Cu*1	O*4	0.11
(111)	T4	O*4	Cr*3	0.03
(111)	T5	O*1	Cr*3	0.03
(111)	T6	Cr*3	O*4	0.07
(111)	T7	O*4	Cu1+Cr1	0.36
(111)	T8	O*3	Cu1+Cr1	0.22

图1 复合金属氧化物CuCr2O4（100）、（110）和（111）表面的最稳定结构（正视图与俯视图）

Fig. 1 The most stable structures on the surfaces of CuCr2O4 (100), (110) and (111) composite metal oxides (front view and top view)

图2 CNCl在复合金属氧化物CuCr2O4(110)表面的13种可能的吸附构型

Fig. 2 13 possible adsorption configurations of CNCl on the surface of CuCr2O4 (110) composite metal oxide

图3 CNCl在复合金属氧化物CuCr2O4(110)、(111)和(100)表面的水解反应路径图

Fig. 3 Scheme of hydrolysis reaction path of CNCl on CuCr2O4 (110), (111) and (100) surfaces

图4 几何优化后的复合金属氧化物CuCr2O4（100）、（110）和（111）氧空位缺陷表面结构

Fig. 4 Surface structure of geometrically optimized composite metal oxide CuCr2O4(100), (110) and (111) with oxygen vacancy defects

表2 复合金属氧化物CuCr2O4（100）、（110）和（111）表面上的氧空位形成能

Table 2 Formation energy of oxygen vacancies on surfaces of CuCr2O4 （100），（110） and （111） composite metal oxides

空位缺陷表面	氧空位形成能/eV
(100)-氧空位-1	3.65
(100)-氧空位-2	3.20
(110)-氧空位	3.73
(111)-氧空位	2.02

图5 CNCl在复合金属氧化物CuCr2O4（100）、（110）和（111）含氧空位缺陷表面的水解反应路径图

Fig. 5 Scheme of hydrolysis reaction path of CNCl on the surface of oxygen vacancy defects in CuCr2O4 (100), (110) and (111) composite metal oxides

表3 CNCl在CuCr2O4各表面最优水解路径比较

Table 3 Comparison of the optimal hydrolysis paths of CNCl on various surfaces of CuCr2O4

表面类型	最优路径类型	决速步反应能 (eV)	是否受氧空位促进
(100)-完美	CHOHNH₂→CHOH+NH₃	2.37	否
(100)-氧空位	NCOOH→NCO₂	2.00	是
(110)-完美	CNCl+H→NC	1.41	否
(110)-氧空位	C→COH	1.62	是
(111)-完美	CNCl→ CNCl+H	2.11	否
(111)-氧空位	CHO→CO	2.61	否

图6 CuCr2O4不同表面和位点下小分子吸附能的本征模型

Fig. 6 Intrinsic model of small molecule adsorption energy on different surfaces and sites of CuCr2O4

图7 CNCl水解中间体在CuCr2O4表面及其含氧空位缺陷表面的关键反应步骤的反应能和生成物中间体吸附能的关系

Fig. 7 The relationship between the reaction energy of the key reaction step of CNCl hydrolysis intermediate on the surface of CuCr2O4 and its oxygen vacancy defects and the adsorption energy of the generated intermediate

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复合金属CuCr₂O₄表面CNCl水解反应机理研究

Study on the hydrolysis reaction mechanism of CNCl on the surface of composite metal CuCr₂O₄

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