Research progress on green flotation depressants for pyrite and computational chemistry of microscopic depressing mechanisms

doi:10.12034/j.issn.1009-606X.225297

Abstract

Abstract:

(1)The limitations of traditional pyrite depressants and future development trends are introduced.

(2)The crystal structure and surface properties of pyrite are described.

(3)The classification and mechanisms of pyrite depressants are summarized.

(4)The application of computational chemistry in pyrite depression research is compared.

Key words: pyrite, depressant, density functional theory, molecular dynamics, mechanism, green mineral processing

摘要：

(1)介绍传统黄铁矿抑制剂的缺点及未来发展趋势。

(2)叙述黄铁矿的晶体结构与表面性质。

(3)列举黄铁矿抑制剂的分类与作用机理。

(4)对比计算化学在黄铁矿抑制研究中的应用。

关键词: 黄铁矿, 抑制剂, 密度泛函理论, 分子动力学, 作用机理, 绿色选矿

CLC Number:

TD951

Dongdong HE, Jian LIU, Rong HUANG, Hong YIN, Puwen FAN. Research progress on green flotation depressants for pyrite and computational chemistry of microscopic depressing mechanisms[J]. The Chinese Journal of Process Engineering, 2026, 26(9): 959-975.

何东东, 刘建, 黄蓉, 尹红, 范璞文. 黄铁矿绿色浮选抑制剂及其微观抑制机理计算化学研究进展[J]. 过程工程学报, 2026, 26(9): 959-975.

Figures/Tables 16

Fig.1 Atomic arrangement structures of the {100} and {111} crystal planes of pyrite (top and side views)[26]

Fig.2 Primary mechanism of lime in depressing pyrite[34]

Table 1 Main oxidation products on the pyrite surface under different pH conditions

pH	Main oxidation products	Surface property	Effect on floatability
Acidic (pH<4)	S⁰, $S O 4 2 ‒$	Hydrophobic	Promotes flotation
Neutral (pH 5~8)	FeOOH, $S 2 O 3 2 ‒$	Moderately hydrophilic	Collector-dependent
Alkaline (pH>9)	Fe(OH)₃, $S O 4 2 ‒$	Strongly hydrophilic	Depresses flotation

Table 1 Main oxidation products on the pyrite surface under different pH conditions

pH	Main oxidation products	Surface property	Effect on floatability
Acidic (pH<4)	S⁰, $S O 4 2 ‒$	Hydrophobic	Promotes flotation
Neutral (pH 5~8)	FeOOH, $S 2 O 3 2 ‒$	Moderately hydrophilic	Collector-dependent
Alkaline (pH>9)	Fe(OH)₃, $S O 4 2 ‒$	Strongly hydrophilic	Depresses flotation

Fig.3 Mechanism of SMA in depressing pyrite[49]

Fig.4 Chemical structures of phenolic compounds, sodium thioglycolate, sodium diethyldithiocarbamate, and bis(carboxymethyl) trithiocarbonate

Fig.5 Possible mechanisms for adsorption of natural depressant on mineral surfaces[52]

Fig.6 Adsorption mechanism of dextrin on the pyrite surface[52]

Table 2 Percentage of Acidithiobacillus ferrooxidans (A. f) coverage on pyrite surface after 15 min in seawater[59]

pH	Attached bacteria/(bacteria/g)	Area of attached bacteria/(m²/g)	Percentage of covered pyrite surface/%
4	2.58×10⁸	1.68×10^-4	1.63
8	1.99×10⁹	1.29×10^-3	12.59

Fig.7 Schematic diagram of selective depressing effect of MFA on pyrite for floating chalcopyrite in weak-alkalinity solution system[60]

Fig.8 Mechanism of PA in selectively depressing pyrite to enable chalcopyrite flotation in solution system at pH≈8[63]

Fig.9 Comparison of the re-activation potential of pyrite after depression

Table 3 The core depression mechanisms, industrial status, and main advantages of pyrite depressants

Comparative aspect	Typical representatives	pH range	Core mechanism	Industrial status	Relative cost	Main advantages	Main limitations	Ref.
Traditional inorganic depressants	Lime, cyanide	High alkalinity	High-alkalinity oxide film/strong complexation adsorption	Widely applied/restricted or banned	Extremely low overall	Low cost, stable performance	High-alkalinity scaling, loss of precious metals, toxicity risk (cyanide)	[59,60]
Organic small-molecule depressants	SMA, PA, L-dopa	Near neutral to weakly alkaline	Functional group chemisorption	Laboratory/pilot-scale testing	Medium-high	High selectivity, molecular designability	High cost, unknown stability, limited case studies	[49-51]
Polymer depressants	Dextrin, carrageenan, CMC	Wide range	Steric hindrance and hydrophilic film	Preliminary industrial application	Low-medium	Green, biodegradable, wide source availability	Difficult selectivity control, significant batch-to-batch variability	[52]
Biological depressants	A.ferrooxidans, MFA	Weakly alkaline	Biofilm barrier/metabolite adsorption	Basic research stage; poor stability	High	Environmentally friendly, mild conditions	Long cycle time, difficulty in maintaining activity, high variability	[59,60]
Low-alkalinity depressants	PA, L-dopa, MFA, KMnO₄, etc.	Near-neutral to weakly alkaline	Specific adsorption	Industrial trial stage	Low-medium	Overcomes drawbacks of high alkalinity, green	Challenging to maintain selectivity in complex pulp	[4, 60-62]

Fig.10 Models of molecules on {100} surface of pyrite after interaction[75]

Fig.11 Optimized configurations of cysteine adsorbed on {100} surface of pyrite [adsorption of -SH (1A/1B), -NH3 (2A/2B), =O (-C=O, 3A/3B), -O (-C-OH, 4A/4B) of cysteine on the S/Fe site of pyrite {100}][76]

Fig.12 (a) Electron density distribution and (b) differential charge density map of NaH2CA adsorbed on {100} surface of pyrite[77]

Table 4 Application of key Materials Studio modules in pyrite depression research

Calculation module	Calculation method	Degree of fit	Primary application focus	Advantages	Limitations	Ref.
Forcite	Molecular dynamics	High	Adsorption configuration optimization, interaction energy calculation	Fast computation speed, suitable for large systems	Force field dependence, incapable of handling electronic structures	[80]
DMol³	Density functional theory (DFT)	High	Density of states, band structure, charge analysis	Capable of processing electronic properties with high accuracy	High computational resource consumption, limited system size	[67]
CASTEP	Plane-wave pseudopotential DFT	High	Band structure, surface adsorption	Applicable to periodic systems, high accuracy	High computational cost, complex parameterization	[81]

References 88

[1]	高永伟, 王志华, 黎卫亮, 等. 热液型金矿床中的黄铁矿矿物学研究综述 [J]. 西北地质, 2019, 52(3): 58-69.
	Gao Y W, Wang Z H, Li W L, et al. A review of pyrite mineralogy in hydrothermal gold deposits [J]. Northwestern Geology, 2019, 52(3): 58-69.
[2]	Han G, Wen S M, Wang H, et al. Interaction mechanism of tannic acid with pyrite surfaces and its response to flotation separation of chalcopyrite from pyrite in a low-alkaline medium [J]. Journal of Materials Research and Technology, 2020, 9(3): 4421-4430.
[3]	Liu M M, Cheng C, Yang L, et al. The low-carbon flotation separation of chalcopyrite from pyrite with a fire-new alkylamine-triazine-dithiol collector [J]. Applied Surface Science, 2023, 640: 158338.
[4]	Wei Q, Dong L Y, Jiao F, et al. The synergistic depression of lime and sodium humate on the flotation separation of sphalerite from pyrite [J]. Minerals Engineering, 2021, 163: 106779.
[5]	Wang C, Liu R, Ahmed Khoso S, et al. Combined inhibitory effect of calcium hypochlorite and dextrin on flotation behavior of pyrite and galena sulphides [J]. Minerals Engineering, 2020, 150: 106274.
[6]	Han G, Wen S M, Wang H, et al. Selective adsorption mechanism of salicylic acid on pyrite surfaces and its application in flotation separation of chalcopyrite from pyrite [J]. Separation and Purification Technology, 2020, 240: 116650.
[7]	Niu X P, Chen J H, Li Y Q, et al. Correlation of surface oxidation with xanthate adsorption and pyrite flotation [J]. Applied Surface Science, 2019, 495: 143411.
[8]	Yao W M, Min X B, Li Q Z, et al. Dissociation mechanism of particulate matter containing arsenic and lead in smelting flue gas by pyrite [J]. Journal of Cleaner Production, 2020, 259: 120875.
[9]	王李鹏, 叶雪均, 江皇义, 等. 被石灰抑制的黄铁矿活化浮选技术进展 [J]. 有色金属科学与工程, 2011, 2(4): 67-70.
	Wang L P, Ye X J, Jiang H Y, et al. Advances in activation flotation of lime-depressed pyrite [J]. Nonferrous Metals Science and Engineering, 2011, 2(4): 67-70.
[10]	Fuchida S, Xue J, Ishida S, et al. Kinetic investigation of initial oxidative dissolution of pyrite in alkaline media (pH 9-12) and influence of Ca and Mg: a fundamental study for pyrite depression in froth flotation [J]. Journal of Sustainable Metallurgy, 2022, 8: 732-741.
[11]	刘承杰, 邵延海, 李金辉, 等. 锌硫分离低碱浮选药剂研究进展 [J]. 矿产保护与利用, 2024, 44(3): 38-48.
	Liu C J, Shao Y H, Li J H, et al. Research advances in reagents for zinc-sulfur separation via low-alkaline flotation [J]. Conservation and Utilization of Mineral Resources, 2024, 44(3): 38-48.
[12]	高扬. 绿色矿山建设碳减排现状及创新路径探析 [J]. 黄金, 2025, 46(8): 99-103.
	Gao Y. Carbon emission reduction in green mine construction: current status and innovative pathways [J]. Gold, 2025, 46(8): 99-103.
[13]	Han W W, Yang H Y, Tong L L. Interaction mechanism of cyanide with pyrite during the cyanidation of pyrite and the decyanation of pyrite cyanide residues by chemical oxidation [J]. International Journal of Minerals, Metallurgy and Materials, 2024, 31(9): 1996-2005.
[14]	Zhao C H, Huang D W, Chen J H, et al. The interaction of cyanide with pyrite, marcasite and pyrrhotite [J]. Minerals Engineering, 2016, 95: 131-137.
[15]	敖顺福. 有色金属硫化矿低碱介质浮选进展 [J]. 矿产保护与利用, 2025, 45(1): 114-126.
	Ao S F. Flotation advances for nonferrous metal sulfide ores in low-alkaline media [J]. Conservation and Utilization of Mineral Resources, 2025, 45(1): 114-126.
[16]	贺壮志, 朱阳戈, 肖巧斌, 等. 低碱下含硫化物的抑硫机理和行为研究现状 [J]. 有色金属(选矿部分), 2023, (4): 156-162.
	He Z Z, Zhu Y G, Xiao Q B, et al. Research status on the mechanism and behavior of sulfur depression by calcium/magnesium-containing minerals under low-alkalinity conditions [J]. Nonferrous Metals (Mineral Processing Section), 2023, (4): 156-162.
[17]	San Martín F, Kracht W, Vargas T. Biodepression of pyrite using Acidithiobacillus ferrooxidans in seawater [J]. Minerals Engineering, 2018, 117: 127-131.
[18]	Cui W Y, Chen J H. Insight into mineral flotation fundamentals through the DFT method [J]. International Journal of Mining Science and Technology, 2021, 31(6): 983-994.
[19]	Zhang L, Guo J Y, Xie Z X, et al. Micro-mechanism of improving low-rank coal flotation by using carboxylic acid collector: a DFT calculation and MD simulation study [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 622: 126696.
[20]	Li L X, Zhang C, Yuan Z T, et al. AFM and DFT study of depression of hematite in oleate-starch-hematite flotation system [J]. Applied Surface Science, 2019, 480: 749-758.
[21]	王纪镇, 荆茂晨, 刘睿华, 等. 黄铁矿晶体断裂机制与表面反应性研究 [J]. 矿物学报, 2024, 44(3): 317-325.
	Wang J Z, Jing M C, Liu R H, et al. Crystal fracture mechanism and surface reactivity of pyrite [J]. Acta Mineralogica Sinica, 2024, 44(3): 317-325.
[22]	Ferreira A R, González-Jiménez J M, Yesares L, et al. Nanogeochemistry of Ni, Co and Cu in zoned marcasite-pyrite crystals [J]. American Mineralogist, 2025, 110(11): 1737-1755.
[23]	Onufrienok V V, Chzhan A V. Investigation of crystal-chemical features of pyrite and conditions of its formation [J]. Russian Journal of Inorganic Chemistry, 2021, 66(7): 1001-1010.
[24]	Tang X Q, Chen Y. A review of flotation and selective separation of pyrrhotite: a perspective from crystal structures [J]. International Journal of Mining Science and Technology, 2022,32(4): 847-863.
[25]	Chanturiya V, Vigdergauz V, Vorobyev S. Duality of pyrite semiconductor properties influence on flotation [C]//ECS Meeting Abstracts. 2020, DOI: 10.1149/MA2010-01/28/1362 .
[26]	Tang B L, Liang J Y, Wen Z L, et al. Insight into the crystal facet-dependent Cr(VI) reduction: a comparative study of pyrite {100} and {111} facets [J]. Journal of Environmental Sciences, 2025, 150: 78-90.
[27]	Du R, Xian H, Wu X, et al. Morphology dominated rapid oxidation of framboidal pyrite [J]. Geochemical Perspectives Letters, 2021, 16: 53-58.
[28]	李玉琼, 陈建华, 陈晔. 空位缺陷黄铁矿的电子结构及其浮选行为 [J]. 物理化学学报, 2010, 26(5): 1435-1441.
	Li Y Q, Chen J H, Chen Y. Electronic structure and flotation behavior of vacancy-defect pyrite [J]. Acta Physico-Chimica Sinica, 2010, 26(5): 1435-1441.
[29]	尹冰一. 黄铁矿的自诱导浮选行为及电化学研究 [J]. 有色金属(选矿部分), 2013, (1): 45-47.
	Yin B Y. Self-induced flotation behavior and electrochemistry of pyrite [J]. Nonferrous Metals (Mineral Processing Section), 2013, (1): 45-47.
[30]	Ozun S, Vaziri Hassas B, Miller J D. Collectorless flotation of oxidized pyrite [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 561: 349-356.
[31]	薛旭东, 张炎. 黄铁矿在酸性、中性和碱性缓冲溶液中电化学氧化机理的研究 [J]. 黄金, 2025, 46(4): 65-71.
	Xue X D, Zhang Y. Electrochemical oxidation mechanism of pyrite in acidic, neutral and alkaline buffer solutions [J]. Gold, 2025, 46(4): 65-71.
[32]	王璐颖, 林森, 任青山, 等. 黄铁矿在不同pH值氯化钠溶液中的电化学氧化机理研究 [J]. 矿物学报, 2025, 45(2): 280-287.
	Wang L Y, Lin S, Ren Q S, et al. Electrochemical oxidation mechanism of pyrite in sodium chloride solutions with different pH values [J]. Acta Mineralogica Sinica, 2025, 45(2): 280-287.
[33]	李强, 李淑菲. 黄铁矿低碱度浮选抑制剂的研究进展 [J]. 中国矿业, 2024, 33(1): 212-217.
	Li Q, Li S F. Research progress on depressants for pyrite flotation under low-alkalinity conditions [J]. China Mining Magazine, 2024, 33(1): 212-217.
[34]	孙伟, 张英, 覃武林, 等. 被石灰抑制的黄铁矿的活化浮选机理 [J]. 中南大学学报(自然科学版), 2010, 41(3): 813-818.
	Sun W, Zhang Y, Qin W L, et al. Activated flotation mechanism of lime-depressed pyrite [J]. Journal of Central South University (Science and Technology), 2010, 41(3): 813-818.
[35]	吴中贤, 陶东平. 黄铁矿浮选药剂及电化学研究进展 [J]. 有色金属(选矿部分), 2025, (5): 1-12.
	Wu Z X, Tao D P. Research advances in reagents and electrochemistry for pyrite flotation [J]. Nonferrous Metals (Mineral Processing Section), 2025, (5): 1-12.
[36]	Sykora S, Cooke D R, Meffre S, et al. Evolution of pyrite trace element compositions from porphyry-style and epithermal conditions at the lihir gold deposit: implications for ore genesis and mineral processing [J]. Economic Geology, 2018, 113(1): 193-208.
[37]	Babedi L, Tadie M, von der Heyden B P, et al. A rest potential study of impurity (As, Au, Ni and Co) bearing synthetic pyrite in alkaline flotation conditions [J]. Minerals Engineering, 2023, 202: 108277.
[38]	Miao Y, Ye G K, Li B B, et al. Influence of pyrite surface defects on xanthate adsorption: a density functional theory perspective [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 694: 134225.
[39]	张强. 黄铁矿浮选的抑制与解抑活化剂研究进展 [J]. 化工矿物与加工, 2023, 52(2): 61-67.
	Zhang Q. Research progress in depressants and activating de-depressants for pyrite flotation [J]. Industrial Minerals & Processing, 2023, 52(2): 61-67.
[40]	李诗浩, 马强, 王龙, 等. 黄铁矿浮选活化机理研究进展 [J]. 矿产综合利用, 2023, (2): 124-130.
	Li S H, Ma Q, Wang L, et al. Research progress on activation mechanism of pyrite flotation [J]. Multipurpose Utilization of Mineral Resources, 2023, (2): 124-130.
[41]	Guo B. The poisoning of pyrite surface upon xanthate adsorption by cyanide in mildly acidic media [J]. Electroanalysis, 2016, 28(4): 724-732.
[42]	Cao Z, Wang P, Zhang W B, et al. Action mechanism of sodium sulfide on flotation of cyanide-depressed pyrite [J]. Transactions of Nonferrous Metals Society of China, 2020, 30(2): 484-491.
[43]	林榜立, 韦新彦, 阙绍娟. 取代氰化钠的新型无毒抑制剂FY02的合成及抑制性能研究 [J]. 有色金属(选矿部分), 2015, (5): 82-86.
	Lin B L, Wei X Y, Que S J. Synthesis and depressing performance of a novel non-toxic depressant FY02 as a substitute for sodium cyanide [J]. Nonferrous Metals (Mineral Processing Section), 2015, (5): 82-86.
[44]	庄杜娟, 许阳芳, 李宇雄. 新疆某高硫铅锌矿在低碱度条件下的浮选分离工艺研究 [J]. 新疆有色金属, 2023, 46(6): 23-25.
	Zhuang D J, Xu Y F, Li Y X. Flotation separation process of a high-sulfur lead-zinc ore from Xinjiang under low-alkalinity conditions [J]. Xinjiang Nonferrous Metals, 2023, 46(6): 23-25.
[45]	谭欣, 朱阳戈, 孙传尧, 等. 硫酸锌添加顺序对乙硫氮在方铅矿和闪锌矿表面吸附的影响 [J]. 有色金属工程, 2022, 12(12): 73-83.
	Tan X, Zhu Y G, Sun C Y, et al. Effect of zinc sulfate addition sequence on adsorption of diethyldithiocarbamate on galena and sphalerite surfaces [J]. Nonferrous Metals Engineering, 2022, 12(12): 73-83.
[46]	Bai X, Liu J, Wen S M, et al. Selective separation of chalcopyrite and pyrite using a novel organic depressant at low alkalinity [J]. Minerals Engineering, 2022, 185: 107677.
[47]	Li W Y, Bai X, Liu J, et al. Mechanism of Cu ion targeting combined with an organic depressant to enhance the flotation depression of pyrite [J]. Langmuir, 2024, 40(49): 26350-26362.
[48]	邱仙辉, 孙传尧, 邱廷省. 鞣酸对方铅矿及黄铁矿的抑制作用 [J]. 东北大学学报(自然科学版), 2015, 36(1): 124-128.
	Qiu X H, Sun C Y, Qiu T S. Depression effect of tannic acid on galena and pyrite [J]. Journal of Northeastern University (Natural Science), 2015, 36(1): 124-128.
[49]	Qin X Y, Liu J, Yu Y L, et al. Novel application of depressant sodium mercaptoacetate in flotation separation of chalcopyrite and pyrite [J]. Advanced Powder Technology, 2023, 34(9): 104141.
[50]	Li Z Y, Wang Y Y, Jia M X, et al. Effect and mechanism of depressant disodium carboxymethyl trithiocarbonate on flotation separation of stibnite and pyrite [J]. Mining, Metallurgy & Exploration, 2022, 39(3): 1267-1275.
[51]	Pan Z C, Cai C, Liang G Y, et al. Pyrolysis liquid of pine wood: a novel efficient depressant of pyrite in galena flotation [J]. Minerals Engineering, 2024, 210: 108642.
[52]	Asimi Neisiani A, Saneie R, Mohammadzadeh A, et al. Polysaccharides-based pyrite depressants for green flotation separation: an overview [J]. International Journal of Mining Science and Technology, 2023, 33(10): 1229-1241.
[53]	彭建城. 某有机抑制剂合成及其在铜硫分离中作用机理研究 [D]. 赣州: 江西理工大学, 2012.
	Peng J C. Synthesis of an organic depressant and study on its action mechanism in copper-sulfur separation [D]. Ganzhou: Jiangxi University of Science and Technology, 2012.
[54]	曹飞, 孙传尧. 硫化矿浮选机理的量子化学研究进展 [J]. 有色金属(选矿部分), 2012, (5): 49-52.
	Cao F, Sun C Y. Research progress on quantum chemistry of sulfide mineral flotation mechanism [J]. Nonferrous Metals (Mineral Processing Section), 2012, (5): 49-52.
[55]	刘润清, 翟启林, 文晓飞, 等. 低碱条件下糊精与钙离子协同作用对闪锌矿与黄铁矿浮选分离的影响 [J]. 中南大学学报(自然科学版), 2024, 55(7): 2447-2455.
	Liu R Q, Zhai Q L, Wen X F, et al. Synergistic effect of dextrin and calcium ions on flotation separation of sphalerite from pyrite under low-alkalinity conditions [J]. Journal of Central South University (Science and Technology), 2024, 55(7): 2447-2455.
[56]	Yang H F, Cao X Y, Luo J H, et al. Adsorption and depression mechanism of carrageenan on chalcopyrite and pyrite for the efficiency flotation separation [J]. Advanced Powder Technology, 2024, 35(10): 104615.
[57]	康文泽, 马子航. 煤系黄铁矿理化性质及浮选脱硫研究进展 [J]. 洁净煤技术, 2022, 28(5): 109-117.
	Kang W Z, Ma Z H. Research progress on physicochemical properties and flotation desulfurization of coal-series pyrite [J]. Clean Coal Technology, 2022, 28(5): 109-117.
[58]	陈雪茹, 吴夏芫, 陈子璇, 等. 纳米硫铁的生物合成及其强化电子传递和污染物去除的研究进展 [J]. 生物加工过程, 2020, 18(3): 295-302.
	Chen X R, Wu X Y, Chen Z X, et al. Research advances in biosynthesis of iron sulfides nanoparticles and their enhancement on electron transfer and contaminant removal [J]. Bioprocess, 2020, 18(3): 295-302.
[59]	San Martín F, Kracht W, Vargas T, et al. Mechanisms of pyrite biodepression with Acidithiobacillus ferrooxidans in seawater flotation [J]. Minerals Engineering, 2020, 145: 106067.
[60]	Shen Z H, Wen S M, Hao J M, et al. Mineral-source fulvic acid as a selective depressant for flotation separation of chalcopyrite from pyrite under weak alkaline conditions [J]. Transactions of Nonferrous Metals Society of China, 2025, 35(1): 313-325.
[61]	梁爽, 路亮, 张行荣. 有机抑制剂在黄铁矿浮选中的研究进展 [J]. 中国矿业, 2020, 29(S2): 300-302.
	Liang S, Lu L, Zhang X R. Research progress of organic depressants in pyrite flotation [J]. China Mining Magazine, 2020, 29(S2): 300-302.
[62]	Cao Q B, Zhang H Y, Yan Y, et al. Flotation separation of pyrite and chalcopyrite with potassium permanganate as a depressant [J]. Chemical Papers, 2024, 78(3): 1761-1773.
[63]	Han G, Wen S M, Wang H, et al. Pyrogallic acid as depressant for flotation separation of pyrite from chalcopyrite under low-alkalinity conditions [J]. Separation and Purification Technology, 2021, 267: 118670.
[64]	Chen S L, Song Z Y, Shen Z H, et al. Flotation separation of chalcopyrite from pyrite using levodopa as a novel depressant under low-alkalinity conditions [J]. Applied Surface Science, 2025, 696: 162965.
[65]	黄有成, 赵礼兵. 无机抑制剂在低碱度铅锌硫分离中的作用研究 [J]. 现代矿业, 2012, 27(1): 23-29.
	Huang Y C, Zhao L B. Role of inorganic depressants in low-alkalinity lead-zinc-sulfur separation [J]. Modern Mining, 2012, 27(1): 23-29.
[66]	代龙富, 刘建, 李达, 等. 基于苯甲羟肟酸的三元组合捕收剂高效浮选白钨矿研究及分子动力学模拟 [J]. 矿产保护与利用, 2024, 44(3): 49-56.
	Dai L F, Liu J, Li D, et al. Efficient flotation of scheelite using a benzohydroxamic acid-based ternary collector combination and molecular dynamics simulation [J]. Conservation and Utilization of Mineral Resources, 2024, 44(3): 49-56.
[67]	代龙富, 刘建, 李达, 等. BHA浮选锡石体系中锌组分活化机理的量子化学计算研究 [J]. 金属矿山, 2023, (8): 111-118.
	Dai L F, Liu J, Li D, et al. Quantum chemical calculation on activation mechanism of zinc components in the BHA-cassiterite flotation system [J]. Metal Mine, 2023, (8): 111-118.
[68]	姚瑶, 徐世红, 郑仁基, 等. 密度泛函理论在矿物浮选领域中的应用 [J]. 中南大学学报(自然科学版), 2025, 56(4): 1259-1274.
	Yao Y, Xu S H, Zheng R J, et al. Application of density functional theory in mineral flotation [J]. Journal of Central South University (Science and Technology), 2025, 56(4): 1259-1274.
[69]	刘思源, 张晨阳, 李凯, 等. 量子化学在氧化锌矿浮选中的应用研究进展 [J]. 有色金属(选矿部分), 2024, (9): 105-120.
	Liu S Y, Zhang C Y, Li K, et al. Research progress on application of quantum chemistry in zinc oxide ore flotation [J]. Nonferrous Metals (Mineral Processing Section), 2024, (9): 105-120.
[70]	Hou H, Cheng W, Li X. Effect of dodecane on the floatability of coal-bearing pyrite and common pyrite: an experimental and molecular simulation study [J]. Applied Surface Science, 2025, 688: 162392.
[71]	Jin J, Miller J D, Dang L X, et al. Effect of surface oxidation on interfacial water structure at a pyrite (100) surface as studied by molecular dynamics simulation [J]. International Journal of Mineral Processing, 2015, 139: 64-76.
[72]	Ke B L, Li Y Q, Chen J H, et al. DFT study on the galvanic interaction between pyrite (100) and galena (100) surfaces [J]. Applied Surface Science, 2016, 367: 270-276.
[73]	Chang Z Y, He B L, Luo Y J, et al. Effects of Au doping on the adsorption of xanthate on pyrite surface in presence of H₂O: a DFT study [J]. Minerals Engineering, 2024, 210: 108667.
[74]	Feng X L, Jian S, Chen H M, et al. Synergistic adsorption of ethyl xanthate and butyl xanthate on pyrite surfaces: a DFT study [J]. International Journal of Quantum Chemistry, 2024,124(15): e27448.
[75]	王瑜, 刘建, 罗德强, 等. 巯基乙酸和巯基乙醇对黄铁矿抑制作用的DFT计算 [J]. 昆明理工大学学报(自然科学版), 2018, 43(2): 39-44.
	Wang Y, Liu J, Luo D Q, et al. DFT calculation on depression effect of thioglycolic acid and mercaptoethanol on pyrite [J]. Journal of Kunming University of Science and Technology (Natural Science Edition), 2018, 43(2): 39-44.
[76]	Zheng X F, Pan X, Nie Z Y, et al. Combined DFT and XPS investigation of cysteine adsorption on the pyrite (100) surface [J]. Minerals (Basel), 2018, 8(9): 366.
[77]	Ling S S, Shang Y B, Wang Y, et al. Selective depression of pyrite by cyanuric acid trisodium salt in chalcopyrite flotation: surface characterization and DFT insights [J]. Applied Surface Science, 2026, 716: 164740.
[78]	Zhang W J, Sun W, Zheng M J, et al. Prediction of collector flotation performance based on machine learning and quantum chemistry: a case of sulfide minerals [J]. Separation and Purification Technology, 2024, 342: 126954.
[79]	Gao Z Y, Wang Q H, Wu Y X, et al. Quantum chemistry assisted screening of zircon flotation collectors [J]. Minerals Engineering, 2022, 189: 107892.
[80]	Zheng Q F, Shen P L, Su C, et al. Selective depression mechanism: surface chemistry and molecular dynamics study on the flotation separation of chalcopyrite and pyrrhotite [J]. Journal of Environmental Chemical Engineering, 2025, 13(6): 119856.
[81]	Luo A R, Chen J H. Low-temperature collector for smithsonite flotation: experiments and DFTB+ study [J]. Colloids and Surfaces A, Physicochemical and Engineering Aspects, 2024, 688: 133651.
[82]	Nieto S, Piceros E, Quezada G R, et al. Experimental and molecular dynamics study of pyrite effects on the flocculation of clayey tailings in seawater [J]. Polymers, 2025, 17(21): 2895.
[83]	Kumar D, Goverapet Srinivasan S, Jain V, et al. Understanding flotation processes at the atomic scale using density functional theory-a case study on adsorption of 2-mercaptobenzothiazole on chalcopyrite and pyrite surfaces [J]. Applied Surface Science, 2022, 579: 152112.
[84]	Li T S, Guo Z H. Mechanisms of arsenic oxidation in the presence of pyrite: an experimental and theoretical study [J]. The Science of the Total Environment, 2024, 921:171072.
[85]	Yeston J. A checkup on density functional theory [J]. Science (American Association for the Advancement of Science), 2017, 356(6342): 1041-1042.
[86]	Shepard C, Zhou R, Bost J, et al. Efficient exact exchange using Wannier functions and other related developments in planewave-pseudopotential implementation of RT-TDDFT [J]. Journal of Chemical Physics, 2024, 161(2): 024111 .
[87]	Xi P, Shi C X, Yan P K, et al. DFT study on the influence of sulfur on the hydrophobicity of pyrite surfaces in the process of oxidation [J]. Applied Surface Science, 2019, 466: 964-969.
[88]	Chen J H, Zhang Y B. Large system study of chalcopyrite and pyrite flotation surfaces based on SCC-DFTB parameterization method [J]. International Journal of Mining Science and Technology, 2025, 35(7): 1037-1055.