改性铝在制氢及去除水中污染物中的应用

doi:10.3969/j.issn.1000-5641.2023.02.018

摘要/Abstract

摘要：

金属铝(Al)因储量丰富且具有较低的氧化还原电位, 在Al-水制氢及水处理领域得到广泛研究, 而Al颗粒表面的致密氧化膜是影响Al还原活性的主要因素. 除了酸/碱溶解、合金化及机械球磨等常见的Al表面处理方法, 近年来出现的Al表面改性技术被认为是一种经济有效且工艺条件相对温和的Al表面活化方法. 本文通过综述Al表面改性方法在Al-水制氢及Al去除水中污染物方面的研究报道, 突出了该方法相比于其他Al表面处理方法所存在的优势及不足. 同时, 对Al表面改性技术在制氢及去除水中污染物中的应用进行了展望, 以期促进Al表面改性技术在制氢及水处理领域的研究进展.

关键词: 铝, 表面改性, 制氢, 去除污染物

Abstract:

Aluminum (Al) used for hydrogen generation and aqueous contaminant removal has been widely studied given its abundance and low redox potential; the reduction ability of Al, moreover, is restricted by the passive surface oxide film on Al particles. In addition to common Al surface treatment methods, such as acid/alkali washing, alloying, and mechanical ball-milling, Al surface modification technology arising in recent years has also been confirmed as an efficient Al activation method given its economical cost and benign manufacturing process. In this study, the merits and disadvantages of surface modification relative to other Al surface treatment methods were highlighted by reviewing existing research on the application of Al surface modification in hydrogen generation and aqueous contaminant removal. In addition, the paper presents an outlook on Al surface modification technology used for hydrogen generation and aqueous contaminant removal to promote the study of related processes.

Key words: aluminum, surface modification, hydrogen generation, contaminant removal

中图分类号:

X703.1

杨阳, 邓振炎, 郭晓晗, 麻根旺, 盖卫卓. 改性铝在制氢及去除水中污染物中的应用[J]. 华东师范大学学报（自然科学版）, 2023, 2023(2): 168-182.

Yang YANG, Zhenyan DENG, Xiaohan GUO, Genwang MA, Weizhuo GAI. Surface-modified aluminum used for hydrogen generation and aqueous contaminant removal[J]. Journal of East China Normal University(Natural Science), 2023, 2023(2): 168-182.

图/表 19

表1

图1

图2

图3

图4

图5

图6

表2

图7

图8

图9

图10

图11

表3

图12

表4

图13

图14

表5

参考文献 61

1	BOKARE A D, CHOI W Y. Review of iron-free Fenton-like systems for activating H₂O₂ in advanced oxidation processes . Journal of Hazardous Materials, 2014, 275, 121- 135.
2	YANG S Y, ZHENG D, CHANG S Y, et al. Zero valent aluminum based oxidation/reduction technology applied in water treatment. Progress in Chemistry, 2016, 28 (5): 754- 762.
3	LIANG J, AZHAR U, MEN P, et al. Fluoropolymer/SiO₂ encapsulated aluminum pigments for enhanced corrosion protection . Applied Surface Science, 2019, 487, 1000- 1007.
4	GAI W Z, ZHANG X H, SUN K X, et al. Hydrogen generation from Al-water reaction promoted by M-B/γ-Al₂O₃(M = Co, Ni) catalyst . International Journal of Hydrogen Energy, 2019, 44 (45): 24377- 24386.
5	GAI W Z, ZHANG X H, SUN K X, et al. Hydrogen generation from Al-water reaction catalyzed by Fe/AlOOH composite. Energy Science & Engineering, 2020, 8 (7): 2402- 2411.
6	YAVOR Y, GOROSHIN S, BERGTHORSON J M, et al. Enhanced hydrogen generation from aluminum-water reactions. International Journal of Hydrogen Energy, 2013, 38 (35): 14992- 15002.
7	SWAMY A K N, SHAFIROVICH E. Conversion of aluminum foil to powders that react and burn with water. Combustion and Flame, 2014, 161, 322- 331.
8	BELITSKUS D. Reaction of aluminum with sodium hydroxide solution as a source of hydrogen. Journal of the Electrochemical Society, 1970, 117, 1097- 1099.
9	PYUN S I, MOON S M. Corrosion mechanism of pure aluminium in aqueous alkaline solution. Journal of Solid State Electrochemistry, 2000, 5 (4): 267- 272.
10	ZHANG J S, KLASKY M, LETELLIER B C. The aluminum chemistry and corrosion in alkaline solutions. Journal of Nuclear Materials, 2009, 384 (2): 175- 189.
11	SOLER L, CANDELA A M, MACANAS J, et al. Hydrogen generation from water and aluminum promoted by sodium stannate. International Journal of Hydrogen Energy, 2010, 35 (3): 1038- 1048.
12	LIN K Y A, LIN C H. Simultaneous reductive and adsorptive removal of bromate from water using acid-washed zero-valent aluminum (ZVAl). Chemical Engineering Journal, 2016, 297, 19- 25.
13	BOKARE A D, CHOI W. Degradation of aqueous organic pollutants. Environmental Science & Technology, 2009, 43, 7130- 7135.
14	LIU W P, ZHANG H H, CAO B B, et al. Oxidative removal of bisphenol A using zero valent aluminum-acid system. Water Research, 2011, 45, 1872- 1878.
15	FU F L, HAN W J, CHENG Z H, et al. Removal of hexavalent chromium from wastewater by acid-washed zero-valent aluminum. Desalination and Water Treatment, 2016, 57 (1/2): 5592- 5600.
16	CHENG Z H, FU F L, PANG Y S, et al. Removal of phenol by acid-washed zero-valent aluminum in the presence of H₂O₂. Chemical Engineering Journal, 2015, 260, 284- 290.
17	ZIEBARTH J T, WOODALL J M, KRAMER R A. Liquid phase-enabled reaction of Al-Ga and Al-Ga-In-Sn alloys with water. International Journal of Hydrogen Energy, 2011, 36 (9): 5271- 5279.
18	WANG W, CHEN D M, YANG K. Investigation on microstructure and hydrogen generation performance of Al-rich alloys. International Journal of Hydrogen Energy, 2021, 35 (21): 12011- 12019.
19	CHEN X Y, ZHAO Z W, LIU X H. Hydrogen generation by the hydrolysis reaction of ball-milled aluminium-lithium alloys. Journal of Power Sources, 2014, 254, 345- 352.
20	CHENG Z H, FU F L, DIONYSIOU D D, et al. Adsorption, oxidation, and reduction behavior of arsenic in the removal of aqueous As(Ⅲ) by mesoporous Fe/Al bimetallic particles. Water Research, 2016, 96, 22- 31.
21	FU F L, CHENG Z H, DIONYSIOU D D, et al. Fe/Al bimetallic particles for the fast and highly efficient removal of Cr(Ⅵ) over a wide pH range: Performance and mechanism. Journal of Hazardous Materials, 2015, 298, 261- 269.
22	FAN M Q, SUN L X, XU F. Feasibility study of hydrogen production for micro fuel cell from activated Al-In mixture in water. Energy, 2010, 35 (3): 1333- 1337.
23	WANG C P, YANG T, LIU Y H. Hydrogen generation by the hydrolysis of magnesium-aluminum-iron material in aqueous solution. International Journal of Hydrogen Energy, 2014, 39 (21): 10843- 10852.
24	PREEZ S D P, BESSARABOV D G. Hydrogen generation of mechanochemically activated Al-Bi-In composites. International Journal of Hydrogen Energy, 2017, 42, 16589- 16602.
25	DREIZIN E L, SCHOENITZ M. Mechanochemically prepared reactive and energetic materials: A review. Journal of Materials Science, 2017, 52 (20): 11789- 11810.
26	RAVAVI-TUOUSI S S, SZPUNAR J A. Effect of structural evolution of aluminum powder during ball milling on hydrogen generation in aluminum-water reaction. International Journal of Hydrogen Energy, 2013, 38 (2): 795- 806.
27	HUANG X N, LV C J, WANG Y, et al. Hydrogen generation from hydrolysis of aluminum/graphite composites with a core-shell structure. International Journal of Hydrogen Energy, 2012, 37 (9): 7457- 7463.
28	WANG H W, CHUNG H W, TENG H T, et al. Generation of hydrogen from aluminum and water-Effect of metal oxide nanocrystals and water quality. International Journal of Hydrogen Energy, 2011, 36 (23): 15136- 15144.
29	CHEN X Y, ZHAO Z W, HAO M M, et al. Research of hydrogen generation by the reaction of Al-based materials with water. Journal of Power Sources, 2013, 222, 188- 195.
30	LIU Y A, WANG X H, LIU H Z, et al. Effect of salts addition on the hydrogen generation of Al-LiH composite elaborated by ball milling. Energy, 2015, 89, 907- 903.
31	FAN M Q, XU F, SUN L X, et al. Hydrolysis of ball milling Al-Bi-hydride and Al-Bi-salt mixture for hydrogen generation. Journal of Alloys and Compounds, 2008, 460 (1/2): 125- 129.
32	DENG Z Y, LIU Y F, TANAKA Y, et al. Modification of Al particle surfaces by γ-Al₂O₃ and its effect on the corrosion behavior of Al . Journal of the American Ceramic Society, 2005, 88 (4): 977- 979.
33	DENG Z Y, FUKASAWA T, ANDO M, et al. High-surface-area alumina ceramics fabricated by the decomposition of Al(OH)₃. Journal of the American Ceramic Society, 2001, 84 (3): 485- 491.
34	DENG Z Y, FUKASAWA T, ANDO M, et al. Bulk alumina support with high tolerant strain and its reinforcing mechanisms. Acta Materialia, 2001, 49 (11): 1939- 1946.
35	DENG Z Y, FUKASAWA T, ANDO M, et al. Microstructure and mechanical properties of porous alumina ceramics fabricated by the decomposition of aluminum hydroxide. Journal of the American Ceramic Society, 2001, 84 (11): 2638- 2644.
36	DENG Z Y, FERREIRA J M F, TANAKA Y, et al. Physicochemical mechanism for the continuous reaction of γ-Al₂O₃ modified aluminum powder with water . Journal of the American Ceramic Society, 2007, 90 (5): 1521- 1526.
37	DENG Z Y, LIU Y F, TANAKA Y, et al. Temperature effect on hydrogen generation by the reaction of γ-Al₂O₃-modified Al powder with distilled water . Journal of the American Ceramic Society, 2005, 88 (10): 2975- 2977.
38	DENG Z Y, LIU W H, GAI W Z. Role of modification agent coverage in hydrogen generation by the reaction of Al with water. Journal of the American Ceramic Society, 2010, 93 (9): 2534- 2536.
39	LIU W H, GAI W Z, DENG Z Y, et al. Enhancing hydrogen-generation performance of γ-Al₂O₃ modified Al powder by ultrasonic dispersion . Journal of the American Ceramic Society, 2012, 95 (4): 1193- 1196.
40	GAI W Z, SHI Y, DENG Z Y, et al. Clarification of activation mechanism in oxide-modified aluminum. International Journal of Hydrogen Energy, 2015, 40, 12057- 12062.
41	GAI W Z, FANG C S, DENG Z Y. Hydrogen generation by the reaction of Al with water using oxides as catalysts. International Journal of Energy Research, 2014, 38, 918- 925.
42	FANG C S, GAI W Z, DENG Z Y. Al surface modification by a facile route. Journal of the American Ceramic Society, 2014, 97 (1): 44- 47.
43	YANG Y, GAI W Z, DENG Z Y, ZHOU J G. Hydrogen generation by the reaction of Al with water promoted by an ultrasonically prepared Al(OH)₃ suspension . International Journal of Hydrogen Energy, 2014, 39, 18734- 18742.
44	YANG Y, GAI W Z, ZHOU J G, et al. Surface modified zero-valent aluminum for Cr(Ⅵ) removal at neutral pH. Chemical Engineering Journal, 2020, 395, 125140- 125147.
45	ZHANG Y X, YANG S Y, ZHANG Y Q, et al. Enhancement of Cr(Ⅵ) removal by mechanically activated micron-scale zero-valent aluminum (MA-mZVAl): Performance and mechanism especially at near-neutral pH. Chemical Engineering Journal, 2018, 353, 760- 768.
46	REN T F, ZHANG Y X, LIU J Q, et al. Ethanol-assisted mechanical activation of zero-valent aluminum for fast and highly efficient removal of Cr(Ⅵ). Applied Surface Science, 2020, 533, 147543- 147552.
47	XIE S, YANG Y, GAI W Z, et al. Oxide modified aluminum for removal of methyl orange and methyl blue in aqueous solution. RSC Advances, 2021, (11): 867- 875.
48	LIU C M, HUANG X Y, ZHANG H Y, et al. The decolouration of methyl orange using aluminum foam, ultrasound and direct electric current. Materials Research Express, 2018, 5 (1): 015501- 015507.
49	SHABBIR S, FAHEEM M, ALI N, et al. Periphyton biofilms: A novel and natural biological system for the effective removal of sulphonated azo dye methyl orange by synergistic mechanism. Chemosphere, 2017, 167, 236- 246.
50	ALJUNDI I H. Bromate formation during ozonation of drinking water: A response surface methodology study. Desalination, 2011, 277, 24- 28.
51	FISCHBACHER A, LÖPPENBERG K, SONNTAG C, et al. A new reaction pathway for bromite to bromate in the ozonation of bromide. Environmental Science & Technology, 2015, 49, 11714- 11720.
52	World Health Organization. Guidelines for Drinking-Water Quality [M]. 4th ed. Geneva: WHO Press, 2011: 324.
53	LIN K Y A. Simultaneous reductive and adsorptive removal of bromate from water using acid-washed zero-valent aluminum (ZVAl) [J]. Chemical Engineering Journal, 2016, 297: 19-25.
54	LIN K Y A, LIN J Y, LIEN H L. Valorization of aluminum scrap via an acid-washing treatment for reductive of toxic bromate from water. Chemosphere, 2017, 172, 325- 332.
55	CHIU T Y, LEE P Y, AFEDZI T W, et al. Elimination of bromate from water using aluminum beverage cans via catalytic reduction and adsorption. Journal of Colloid and Interface Science, 2018, 532, 416- 425.
56	ZHOU W, YANG Y, GAI W Z, et al. A comparative study on high-efficient reduction of bromate in neutral solution using zero-valent Al treated by different procedures. The Science of the Total Environment, 2021, 795, 148786- 148794.
57	XIE L, SHANG C L. Effects of copper and palladium on the reduction of bromate by Fe(0). Chemosphere, 2006, 64 (6): 919- 930.
58	LIN K Y A, LIN C H, LIN J L. Efficient reductive elimination of bromate in water using zero-valent zinc prepared by acid-washing treatments. Journal of Colloid and Interface Science, 2017, 504, 397- 403.
59	LIN K Y A, LIN C H, YANG H T. Enhanced bromate reduction using zero-valent aluminum mediated by oxalic acid. Journal of Environmental Chemical Engineering, 2017, 5 (5): 5085- 5090.
60	WU S, YANG S Y, LIU S J, et al. Enhanced reactivity of zero-valent aluminum with ball milling for phenol oxidative degradation. Journal of Colloid and Interface Science, 2020, 560, 260- 272.
61	United States Eenvironmental Protection Agency (US EPA). EPA non-regulatory health-based drinking water levels [EB/OL]. (2014-04-01)[2021-10-13]. http://water.epa.gov/drink/standards/hascience.cfm#dw-strandards.

零价金属	标准氧化还原电位(E₀ )/ V
Al³⁺/ Al⁰	–1.662
Zn²⁺/ Zn⁰	–0.762
Fe²⁺/ Fe⁰	–0.440
Cu²⁺/ Cu⁰	–0.337
H⁺/ H₂	0

处理方法	反应条件	产氢效率/%	反应时间/h	参考文献
Alkaline additive	0.25 mol/L Na₂SnO_3, pH 12.0, 75℃, 1.01 × 10⁵ Pa	35	~ 0	[11]
Alloys	50 wt% Al-34 wt% Ga-11 wt% In-5 wt% Sn, 55℃, 1.01 × 10⁵ Pa	85	~ 0	[17]
Ball-milled alloys	Al-5 wt% Li-5 wt% NaCl, 25℃, 1.01 × 10⁵ Pa	100	16.67	[19]
Ball-milled Al/C	Al-23 wt% C-2 wt% NaCl, 65℃, 1.01 × 10⁵ Pa	86	5.83	[27]
GMAPs	30 wt% Al : 70 wt% γ-Al₂O₃, 25℃, 1.01 × 10⁵ Pa	28	~ 22	[32]
Direct addition	30 vol% γ-Al₂O₃, 25℃, 4 kPa	~ 100	~ 20	[41]
Direct addition	30 vol% α-Al₂O₃, 25℃, 4 kPa	~ 100	~ 38	[41]
Direct addition	30 vol% TiO₂, 25℃, 4 kPa	~ 100	~ 31	[41]
Direct addition	30 vol% Al(OH)₃, 25℃, 4 kPa	~ 100	~ 22	[41]

处理方法	反应条件	去除效率/%	反应时间/min	参考文献
Acid washing	[Cr(Ⅵ)]₀ = 20.0 mg/L, [Al]₀ = 0.4 g/L, pH₀ = 1.5	100	150	[15]
Al deposited with Fe	[Cr(Ⅵ)]₀ = 20.0 mg/L, [Fe/Al]₀ = 6.0 g/L, Fe/Al mass ratio: 0.75 g, pH₀ = 3.0	100	10	[21]
GMAPs	[Cr(Ⅵ)]₀ = 8 mg/L, [Al]₀ = 4 g/L, near neutral pH,	100	60	[44]
Ball milling	5.0 wt% NaCl (grinding aid), 300 r/min, 1.0 h, N₂, [Cr(Ⅵ)]₀ = 0.2 mmol/L, [Al]₀ = 4 g/L, pH₀ = 7.00	100	380	[45]
Ball milling	Ethanol (grinding aid), 3.00 h, [Cr(Ⅵ)]₀ = 20 mg/L, [Al]₀ = 4 g/L, near neutral pH	100	25	[46]

材料	反应条件	降解效率/%	反应时间/h	参考文献
GMAPs	Dosage 1 g/L, pH 5.9, C₀20 mg/L, T 45℃	100	1 (M-orange)	[47]
GMAPs	Dosage 1 g/L, pH 5.7, C₀20 mg/L,T 45℃	96	2.5 (M-blue)	[47]
Aluminum foam	pH 7.2, C₀20 mg/L, with ultrasound and direct electric current	100	8 (M-orange)	[48]
Periphyton	Dosage 4 g/L, pH 7.0, C₀50 mg/L, T 30℃	70	168 (M-orange)	[49]

[1]	张旭, 黄定江. 基于深度学习的铝材表面缺陷检测[J]. 华东师范大学学报（自然科学版）, 2020, 2020(6): 105-114.
[2]	廖斌;安同一;王源身;朱守正. 微波等离子体用于橡胶表面改性处理的研究[J]. 华东师范大学学报(自然科学版), 2003, 2003(2): 40-45.
[3]	李敏;王振领;单永奎;戴立益;. 钛铝硅复合氧化物的合成及应用研究 [J]. 华东师范大学学报(自然科学版), 2003, 2003(2): 99-101.