Progress on the Photocatalytic Reduction Removal of Chromium
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Personal Account DOI: 10.1002/tcr.201800153 1 2 3 4 THE 5 CHEMICAL Progress on the Photocatalytic Reduction 6 7 RECORD Removal of Chromium Contamination 8 9 10 11 Zengying Zhao,[a] He An,[a] Jing Lin,*[b] Mingchao Feng,[a] Vignesh Murugadoss,[c, d, e] [e] [c, f] [g] [h] [i] [j] 12 Tao Ding,* Hu Liu, Qian Shao, Xianmin Mai,* Ning Wang, Hongbo Gu, [d] [c] 13 Subramania Angaiah,* and Zhanhu Guo* 14 15 16 17 Abstract: Rapid industrialization leads to increased wastewater discharge encompassing 18 hexavalent chromium (Cr(VI)), which leads to serious environmental problems of toxicity and 19 potential carcinogenicity. Removal of these species is normally carried out by ion-exchange, 20 precipitation, membrane filtration, sorption, photocatalytic reduction, etc. This review mainly focuses on the photocatalytic and photoelectrocatalytic (PEC) reduction of Cr (VI), because of 21 their advantages over other methods such as reduced risk of secondary pollution by non-reduced 22 Cr (VI), no sludge formation, no need for a large amount of chemical reagents, clean and easy 23 installation. The main factors influencing the photocatalytic reduction efficiency of Cr (VI) such 24 as catalyst activity, solution pH, Cr adsorption on the catalyst and additives, are briefly discussed. 25 Finally, a special emphasis is provided to the photoelectrocatalytic (PEC) reduction of Cr (VI). 26 Keywords: Chromium removal, Photocatalytic reduction, Photoelectrocatalytic reduction 27 28 29 1. Chromium Pollution 30 surface and groundwater is becoming a serious concern due 31 Chromium (Cr) is one of the most important industrial raw to emissions from industrial processes. Due to the danger to 32 materials, used in leather tanning, electroplating, metal the environment and the accumulation in the food chain, the 33 finishing, magnetic tapes, pigments, electrical or electronic removal of Cr attracts increasing attention.[2] For example, it 34 equipment, and catalysis, etc.[1] Chromium contamination in is one of the sixteen most toxic pollutants because of its 35 36 [a] Z. Zhao, H. An, M. Feng [f] H. Liu 37 School of Science, China University of Geosciences, Beijing 100083, Key Laboratory of Materials Processing and Mold (Zhengzhou 38 China University), Ministry of Education; National Engineering Research 39 [b] J. Lin Center for Advanced Polymer Processing Technology, Zhengzhou 40 School of Chemistry and Chemical Engineering, Guangzhou University, Zhengzhou, 450002, China University, Guangzhou 510006, China [g] Q. Shao 41 E-mail: [email protected] College of Chemical and Environmental Engineering, Shandong 42 [c] V. Murugadoss, H. Liu, Z. Guo University of Science and Technology, Qingdao, Shandong, 266590, 43 Chemical and Biomolecular Engineering Department, China 44 University of Tennessee, Knoxville, TN 37996, USA [h] X. Mai E-mail: [email protected] School of Urban Planning and Architecture, Southwest Minzu 45 [d] V. Murugadoss, S. Angaiah University, Chengdu 610041, China 46 Electrochemical Energy Research Lab, Centre for Nanoscience and E-mail: [email protected] 47 Technology, Pondicherry University, Puducherry-605 014, India [i] N. Wang 48 E-mail: [email protected] State Key Laboratory of Marine Resource Utilization in South China 49 [e] V. Murugadoss, T. Ding Sea, Hainan University, Haikou 570228, China College of Chemistry and Chemical Engineering, Henan University, [j] H. Gu 50 Kaifeng 475004, China Shanghai Key Lab of Chemical Assessment and Sustainability, 51 E-mail: [email protected] Department of Chemistry, Tongji University, Shanghai 200092, 52 China Chem. Rec. 2019, 19, 873–882 © 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 873 Personal Account THE CHEMICAL RECORD 1 teratogenic and carcinogenic effect on human health,[3] and modified for the adsorption of Cr(VI).[14a,c] Some examples 2 has also been recognized by the United State Environmental are as follows: 3 Protection Agency (USEPA) as Group A carcinogen.[4] There- 4 fore, the USEPA and the World Health Organization 3.1. Organomodified Diatomaceous Earth 5 (WHO) have set the maximum contaminant levels (MCL) in 6 drinking water at 0.1 mg/L and 0.05 mg/L for chromium.[5] Diatomaceous earth (DAT) has been used in the removal of À [20] 7 Chromium presents as bichromate (HCrO4 ) or chromate Cr(VI). The adsorption capacity of DAT was improved 2À 8 (CrO4 ) in water system depending on their pH and the using a cationic surfactant, hexadecyltrimethylammonium 9 Cr(VI) is negatively charged in all forms. At pH <6.8, the bromide (HDTMABr), by ion exchange reaction. The Cr(III) À 10 HCrO4 and H2CrO4 are predominantly present, while at and Cr(VI) ions were adsorbed onto natural DAT and 2À [6] 11 pH > 6.8, CrO4 alone is stable. The oxy-anions in the organomodified DAT-HDTMABR from aqueous solutions. 2À 12 CrO4 are reduced to their trivalent form Cr(III) by The adsorption process is relatively faster and the equilibrium 13 accepting electrons from the reducing reagents present in the is established quicker for DAT-HDTMABR than for DAT. 14 solution. The rate of Cr(VI) reduction increases with the The results show that organomodified diatomaceous earth has 15 decrease in pH of the solution. The reduced Cr(III) is less more metal ion removal (%R) and adsorption capacity than 16 toxic than the Cr(VI). Hence, the reduction of Cr(VI) to the natural material. Therefore, the authors concluded that 17 Cr(III) is not a thorough solution as its toxicity poses a threat the ion-exchange mechanism of the modified method is 18 to the environment and human health. Since Cr(III) is feasible.[4b,21] 19 comparatively more stable with respect to the oxidation- 20 reduction potential, it cannot be easily reduced.[7] Therefore, 3.2. Nano-g-Al O by the Novel Sol-Gel Method 21 the reduction of Cr(VI) to Cr(III) and simultaneous 2 3 22 adsorption of the reduced Cr (III) could be the feasible Al2O3 has been adopted in Cr(VI) removal for several 23 solution for effective chromium removal.[8] At pH 8 or higher, cases.[22] Recently, Shokati et al. prepared a novel nano-g- 24 Cr(III) can react easily with particulates to form insoluble Al2O3 adsorbent using the sol-gel method. The adsorption [9] 25 metal salts such as Cr(OH)3 in water. isotherms for Cr(VI) well fitted with the Langmuir adsorp- 26 tion isotherm equations. The adsorbent has a good capacity 27 2. Chromium Pollution Treatment Methods to adsorb Cr(VI) with a maximum capacity of 13.3 mg/g. 28 The sorption capacity doesn’t change remarkably after reusing 29 Although Cr exists in several valence states (from À2to+ 6), the sorbent for sorption-desorption cycle, so the synthesized 3+ 6+ 30 the less toxic Cr and more toxic Cr are the major nano-g-Al2O3 can be reusable with high efficiency and can be 31 pollutants found in the environment.[10] As for the removal of used in water and wastewater treatment for Cr(VI) remov- 32 Cr(VI), the methods have involved in the use of cationic and al.[14a] 33 anionic ion-exchange resins,[11] chemical precipitation,[12] 34 membrane filtration,[13] sorption,[14] biological method,[15] and 3.3. Modified Magnetic Iron Oxide 35 photocatalytic reduction.[16] 36 However, no perfect methods can overcome the problems Although the synthesis of magnetite nanoparticles is tedious, 37 completely from the pollution treatment cost, process it is still the best adsorbent for Cr(VI) from wastewater.[23] 38 complexity, damage to the environment and removal This is attributed to their high gradient magnetic field that 39 efficiency. Thereinto, the photocatalytic reduction method is improves the separation of the liquid-solid mixture.[24] 40 a kind of green, low-cost method. But the efficiency needs to Sponge-like carbon matrix consists of zerovalent iron nano- 41 be urgently improved. particles following the pseudo-second order and Langmuir 42 isotherm towards Cr(VI) removal. It was observed that the 43 3. Some New Adsorbent Materials for Cr Pollution chromium removal capacity increased with increasing the 44 annealing temperature from 500 to 8008C at the optimum 45 Adsorption methods are preferred to various conventional pH of 3.0. This is attributed to the improved amorphous 46 methods for Cr (VI) removal due to less expensive. In recent nature of the carbon with more disordered bonds and 47 years, research interest focuses on low-cost adsorbents such as magnetic property of zerovalent iron nanoparticles at a higher 48 activated carbon.[16a,17] Especially, because of the low cost and annealing temperature.[13b,25] The new tendency in this field is 49 local availability, natural materials such as chitosan,[18] the magnetic nanoparticles (MNPs) composited with a 50 gum,[15b] fungal mycelia,[15c] sulfate-reducing bacteria,[19] or surfactant or environment-friendly natural polymers, such as 51 certain waste products from industrial operations are a polysaccharide, etc. The hydrogel nanocomposites com- 52 prised of Gum karaya-grafted poly (acrylamide-co-acrylic Chem. Rec. 2019, 19, 873–882 © 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 874 Personal Account THE CHEMICAL RECORD 1 acid) and an iron oxide magnetic exhibited great potential Firstly, the Cr(VI) adsorbed on the surface of the PANI based 2 towards Cr(VI) ions removal as an adsorbent, to improve the composites is reduced to Cr(III) by their amine groups. Later, 3 quality of mine effluents prior to discharge in the environ- the composites can be regenerated by removing the electro- 4 ment.[15b] statically adsorbed Cr(III) by the acid treatments. 5 6 3.4. PAN-FeCl Composite Adsorbent 7 2 4. Photocatalytic Reduction for the Cr(VI) 8 Nanoparticle adsorbents are easier to be prepared compared Removal 9 with the above adsorbents, but the small particle size often 4.1.