盐酸在黄铜矿表面吸附机制的第一性原理计算

doi:10.12034/j.issn.1009-606X.220175

过程工程学报 ›› 2021, Vol. 21 ›› Issue (7): 836-846.DOI: 10.12034/j.issn.1009-606X.220175CSTR: 32067.14.jproeng.220175

盐酸在黄铜矿表面吸附机制的第一性原理计算

李小亮¹^,²(), 田国才¹^,²()

^1.昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室，云南昆明 650093
^2.昆明理工大学冶金与能源工程学院，云南昆明 650093

收稿日期:2020-06-08 修回日期:2020-09-03 出版日期:2021-07-28 发布日期:2021-07-27
通讯作者: 田国才 1609488137@qq.com;tiangc01@163.com
作者简介:李小亮(1993-)，男，江西省吉安市人，硕士研究生，冶金工程专业，E-mail: 1609488137@qq.com
田国才，通讯联系人， E-mail: tiangc01@163.com.
基金资助:
国家自然科学基金资助项目(51774158);云南省中青年学术技术带头人后备人才培养项目(2011CI013)

First-principles calculation of adsorption mechanism of hydrochloric acid on chalcopyrite surface

Xiaoliang LI¹^,²(), Guocai TIAN¹^,²()

^1.State Key Laboratory of Complex Non-ferrous Metal Resource Clean Utilization, Kunming University of Science and Technology, Kunming, Yunnan 650093, China
^2.Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650093, China

Received:2020-06-08 Revised:2020-09-03 Online:2021-07-28 Published:2021-07-27
Contact: Guocai TIAN 1609488137@qq.com;tiangc01@163.com

摘要/Abstract

摘要：

采用第一性原理对盐酸在黄铜矿表面不同位点的吸附及反应机理进行研究。结果表明，黄铜矿(001)-S表面重构后形成了二硫化物S₂^2-。盐酸以解离形式在黄铜矿的(001)硫终止面(001)-S上吸附，浸出过程中H⁺在黄铜矿(001)-S表面上S位点的吸附都会破坏黄铜矿表面所形成的S₂^2-。Cl^-的吸附对黄铜矿(001)-S表面结构也会造成一定的破坏，吸附过程中H⁺和Cl^-与黄铜矿表面发生化学反应生成了FeCl₂和H₂S，这些都有利于黄铜矿的浸出。

关键词: 黄铜矿, 盐酸, 表面吸附, 第一性原理

Abstract:

The leaching of chalcopyrite has always been the core of copper sulfide hydrometallurgy, but chalcopyrite is a sulfide mineral that is difficult to be oxidized and decomposed. At present, a large number of macroscopic phenomena are obtained by focusing on experimental research, and the mechanism is mostly inferred. However, the lack of information on atomic or molecular level hinders the clear and effective explanation to these macroscopic phenomena. Therefore, it is necessary to study the surface interaction between liquid medium and chalcopyrite and the influence of medium on the formation of surface products by means of atomic or molecular level calculation and analysis, which are of great significance to reveal the reaction mechanism of leaching process and improve or develop a green hydrometallurgical technology of chalcopyrite. As a common leaching agent, hydrochloric acid can be used in the leaching of chalcopyrite, and it has been widely studied because of its advantages of recyclable leaching agent, high solubility of metal ions, good oxidation reduction performance and fast leaching rate. In this work, the adsorption and reaction mechanism of hydrochloric acid on different sites of chalcopyrite surface were studied with first-principles calculation. It was shown that the reconstructed sulfur terminated chalcopyrite (001) surface [labeled as (001)-S surface] led to the formation of disulphide S₂^2-. Hydrochloric acid was adsorbed on the sulfur terminated surface (001)-S of chalcopyrite in the form of dissociation. In the process of leaching, the adsorption of H⁺ on sulfur terminated surface (001)-S of chalcopyrite destroyed the S₂^2- formed on the surface. The surface structure of chalcopyrite (001)-S was destroyed by adsorption of chloride ion Cl^-. During the adsorption process, the chemical reactions between H⁺ and Cl^- with the surface of chalcopyrite produce the FeCl₂ and H₂S, which were both beneficial to the leaching of chalcopyrite. The results can provide a theoretical basis and guidance for future research.

Key words: chalcopyrite, hydrochloric acid, surface adsorption, first-principles

中图分类号:

TF811

李小亮, 田国才. 盐酸在黄铜矿表面吸附机制的第一性原理计算[J]. 过程工程学报, 2021, 21(7): 836-846.

Xiaoliang LI, Guocai TIAN. First-principles calculation of adsorption mechanism of hydrochloric acid on chalcopyrite surface[J]. The Chinese Journal of Process Engineering, 2021, 21(7): 836-846.

图/表 16

图1 优化后的黄铜矿晶胞(单位：°)

Fig.1 The optimized unit of chalcopyrite (unit: °)

表1 优化后黄铜矿体相的几何参数 (nm)

Table 1 Geometrical parameters of the chalcopyrite bulk after optimized

Parameter	This work	PWscf^[32]	VASP^[33]	Siesta^[29]	Experimental values^[12]
a=b	0.5256	0.5263	0.5279	0.5277	0.5289
c	1.0395	1.0362	1.0364	1.0447	1.0423
Fe-S	0.2229	0.2241	0.2257	0.2250	0.2257
Cu-S	0.2307	0.2293	0.2287	0.2300	0.2302
Fe-Fe	0.3696	0.3693	-	-	0.3713
Cu-Cu	0.3696	0.3693	-	-	0.3713
Fe-Cu	0.3716	0.3721	-	-	0.3740
S-S	0.3622	0.3659	-	-	0.3685

图2 黄铜矿(001)-S表面(单位为nm)

Fig.2 The chalcopyrite (001)-S surface (unit: nm)

表2 重构的黄铜矿(001)-S表面(单位为nm) (nm)

Table 2 Reconstructed chalcopyrite (001)-S surface

Parameter	This work	Siesta^[29]	VASP^[33]	PWscf^[32]
S-S	0.220	0.223	0.2242	0.2158
Fe-S	0.214	0.224	0.2182	0.2319
Cu-S	0.235	0.230	0.2359	0.2326

图3 黄铜矿(001)-S表面的电子密度图

Fig.3 The electron density of chalcopyrite (001)-S surface

图4 黄铜矿(001)-S表面的吸附位点(单位为nm)

Fig.4 The adsorption sites of chalcopyrite (001)-S surface (unit: nm)

图5 黄铜矿(001)-S表面的态密度图

Fig.5 Density of states of chalcopyrite (001)-S surface

图6 黄铜矿(001)-S表面Fe和S原子的分态密度图

Fig.6 Partial density of states of Fe and S atoms on chalcopyrite (001)-S surface

表3 盐酸在解离情况下H+在不同吸附位点的吸附能和Fe-Cl键长

Table 3 The adsorption energy and Fe-Cl bond length considering different adsorption sites for H+ in the dissociation of hydrochloric acid

Adsorption site for H⁺	ΔΕ/(kcal/mol)	Distance of Fe-Cl/nm	Siesta^[30]
1	-19.4	0.232	-19.2
2	-19.5	0.231	-19.3
3	-14.4	0.227	-14.5
4	-12.8	0.230	-11.9
5	-20.9	0.230	-21.2
6	-20.0	0.232	-21.0
7	-13.5	0.230	-14.6
8	-10.6	0.229	-

图7 盐酸以解离形式吸附在黄铜矿(001)-S表面最稳定的构型(单位：nm)

Fig.7 The most stable configuration with dissociative adsorption of hydrochloric acid on chalcopyrite (001)-S surface (unit: nm)

图8 Cl-发生迁移的吸附位点的优化后的构型(单位：nm)

Fig.8 The optimized configuration with Cl- migrated on the adsorption site (unit: nm)

图9 两个盐酸分子解离吸附在黄铜矿(001)-S表面的最稳定构型及优化后的H2S分子和FeCl2晶体(单位为nm)

Fig.9 The most stable configuration of two hydrochloric acid molecules dissociated and adsorbed on chalcopyrite (001)-S surface and H2S molecule and FeCl2 crystal optimized (unit: nm)

图10 两个盐酸分子解离吸附在黄铜矿(001)-S表面的电子密度图

Fig.10 The electron density of two hydrochloric acid molecules dissociated and adsorbed on chalcopyrite (001)-S surface

图11 两个盐酸分子解离吸附在黄铜矿(001)-S表面前后Fe和S原子的分态密度分析(虚线表示的是费米能级)

Fig.11 PDOS analysis of Fe and S atoms before and after two hydrochloric acid molecules dissociative adsorption on chalcopyrite (001)-S surface (the dash lines represent Fermi level)

图12 盐酸解离吸附在黄铜矿(001)-S表面前后及优化后的H2S分子和FeCl2晶体的分态密度分析

Fig.12 PDOS analysis of hydrochloric acid before and after dissociative adsorption on chalcopyrite (001)-S surface and the H2S molecule and FeCl2 crystal optimized

表4 盐酸解离吸附在黄铜矿(001)-S表面前后各原子的Mulliken电荷布局

Table 4 Mulliken charge population of atoms before and after dissociative adsorption of hydrochloric acid on chalcopyrite (001)-S surface

Atom	Adsorption	S orbital, s/e	P orbital, p/e	D orbital, d/e	Total	Charge/e
H	Before	0.66	0.00	0.00	0.66	0.34
H	After	0.91	0.00	0.00	0.91	0.09
Cl	Before	1.93	5.41	0.00	7.34	-0.34
Cl	After	1.95	5.35	0.00	7.29	-0.29
S5	Before	1.87	4.27	0.00	6.14	-0.14
S5	After	1.85	4.38	0.00	6.23	-0.23
Fe	Before	0.36	0.50	6.94	7.79	0.21
Fe	After	0.37	0.50	6.91	7.77	0.23

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盐酸在黄铜矿表面吸附机制的第一性原理计算

First-principles calculation of adsorption mechanism of hydrochloric acid on chalcopyrite surface

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