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Elucidating the origin mechanism of a morphology-dependent layered double hydroxide catalyst toward organic contaminant oxidation via persulfate activation

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Abstract

Understanding how the morphology of a layered double hydroxide (LDH)–based catalyst alters its catalytic activity provides an available strategy for the rational design and fabrication of high-efficiency catalysts at a micro-scale. Herein, three nickel–iron layered double hydroxide (NiFe-LDH) catalysts including 2D-plate-like hexagon (P-NiFe-LDH), 2D/3D-flower-like solid sphere (FS-NiFe-LDH), and 2D/3D-flower-like hollow sphere (FH-NiFe-LDH) with regulable oxygen vacancies (OVs) were fabricated via a morphological regulation method of Ostwald ripening. The experimental results demonstrated that the three types of NiFe-LDH exhibited different abilities to activate persulfate (PS) for the abatement of acid orange 7 (AO7) with a sequence of FH-NiFe-LDH > FS-NiFe-LDH > P-NiFe-LDH. Particularly, the FH-NiFe-LDH with a hollow structure exhibited the most considerable activity with the first-order rate constant up to k = 0.02639 min−1, benefiting from the highly accessible surface areas, higher intrinsic activity of the exposed crystal planes, and abundant OVs. Characterizations further confirmed that these properties could profoundly allow for more exposure of active sites and enhance the reactivity of OV-connected Ni or Fe to facilitate electron transfer and generate more reactive radicals, therefore elucidating the morphologic origin of catalytic performance. Based on the quenching experiments, sulfate radicals (SO4·−), hydroxyl radicals (·OH), and oxygen radicals (O2·−) were identified to be involved in the decomposition process. Furthermore, the continuous redox cycle of Ni(II)/Ni(III)/Ni(II) and Fe(II)/Fe(III)/Fe(II) was responsible for the generation of active radicals via activating PS.

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References

  • Atienzar P, de Victoria-Rodriguez M, Juanes O, Rodríguez-Ubis JC, Brunet E, García HJE (2011) Layered γ-zirconium phosphate as novel semiconductor for dye sensitized solar cells: improvement of photovoltaic efficiency by intercalation of a ruthenium complex-viologen dyad. Energy Environ Sci 4:4718–4726

    Article  CAS  Google Scholar 

  • Bu Y, Li H, Yu W, Pan Y, Li L, Wang Y, Pu L, Ding J, Gao G, Pan BJES (2021) Peroxydisulfate activation and singlet oxygen generation by oxygen vacancy for degradation of contaminants. Environ Sci Technol 55:2110–2120

    Article  CAS  Google Scholar 

  • Devi LG, Srinivas MJJ (2017) Hydrothermal synthesis of reduced graphene oxide-CoFe2O4 heteroarchitecture for high visible light photocatalytic activity: exploration of efficiency, stability and mechanistic pathways. J Environ Chem Eng 5:3243–3255

    Article  CAS  Google Scholar 

  • Dong H, Zhang X, Li J, Zhou P, Yu S, Song N, Liu C, Che G, Li C (2020) Construction of morphology-controlled nonmetal 2D/3D homojunction towards enhancing photocatalytic activity and mechanism insight. Appl Catal B 263:118270

  • Duan X, Sun H, Shao Z, Wang S (2018a) Nonradical reactions in environmental remediation processes: uncertainty and challenges. Appl Catal B 224:973–982

    Article  CAS  Google Scholar 

  • Duan X, Sun H, Wang S (2018b) Metal-free carbocatalysis in advanced oxidation reactions. Acc Chem Res 51:678–687

    Article  CAS  Google Scholar 

  • Duan X, Kang J, Tian W, Zhang H, Ho S-H, Zhu Y-A, Ao Z, Sun H, Wang S (2019) Interfacial-engineered cobalt@ carbon hybrids for synergistically boosted evolution of sulfate radicals toward green oxidation. Appl Catal B 256:117795

  • Fang P, Wang Z, Wang W (2019) Enhanced photocatalytic performance of ZnTi-LDHs with morphology control. Cryst Eng Comm 21:7025–7031

    Article  CAS  Google Scholar 

  • Gao C, Yu X-Y, Luo T, Jia Y, Sun B, Liu J-H, Huang X (2014) Millimeter-sized Mg–Al-LDH nanoflake impregnated magnetic alginate beads (LDH-n-MABs): a novel bio-based sorbent for the removal of fluoride in water. J Mater Chem A 2:2119–2128

    Article  CAS  Google Scholar 

  • Guo XX, Hu TT, Meng B, Sun Y, Han Y-F (2020) Catalytic degradation of anthraquinones-containing H2O2 production effluent over layered Co-Cu hydroxides: defects facilitating hydroxyl radicals generation. Appl Catalysis B 260:118157

    Article  CAS  Google Scholar 

  • Han X, Yuan A, Yao C, Xi F, Liu J, Dong X (2019) Synergistic effects of phosphorous/sulfur co-doping and morphological regulation for enhanced photocatalytic performance of graphitic carbon nitride nanosheets. J Mater Sci 54:1593–1605

    Article  CAS  Google Scholar 

  • Hodges BC, Cates EL, Kim J-H (2018) Challenges and prospects of advanced oxidation water treatment processes using catalytic nanomaterials. Nat Nanotechnol 13:642–650

    Article  CAS  Google Scholar 

  • Hong Y, Peng J, Zhao X, Yan Y, Lai B, Yao G (2019) Efficient degradation of atrazine by CoMgAl layered double oxides catalyzed peroxymonosulfate: optimization, degradation pathways and mechanism. Chem Eng J 370:354–363

    Article  CAS  Google Scholar 

  • Huang P, Liu J, Wei F, Zhu Y, Wang X, Cao C, Song W (2017) Size-selective adsorption of anionic dyes induced by the layer space in layered double hydroxide hollow microspheres. Mater Chem Front 1:1550–1555

    Article  CAS  Google Scholar 

  • Huang L, Zou Y, Chen D, Wang S (2019) Electronic structure regulation on layered double hydroxides for oxygen evolution reaction. Cinese J Catal 40:1822–1840

    Article  CAS  Google Scholar 

  • Ike IA, Linden KG, Orbell JD, Duke M (2018) Critical review of the science and sustainability of persulphate advanced oxidation processes. Chem Eng J 338:651–669

    Article  CAS  Google Scholar 

  • Jia J, Yang W, Zhang P, Zhang J (2017) Facile synthesis of Fe-modified manganese oxide with high content of oxygen vacancies for efficient airborne ozone destruction. Appl Catal A 546:79–86

    Article  CAS  Google Scholar 

  • Li Y, Shen W-J (2014) Morphology-dependent nanocatalysts: rod-shaped oxides. Chem Soc Rev 43:1543–1574

    Article  Google Scholar 

  • Li M, Chen S, Ni F, Wang Y, Wang L (2008) Layered double hydroxides functionalized with anionic surfactant: direct electrochemistry and electrocatalysis of hemoglobin. Electrochim Acta 53:7255–7260

    Article  CAS  Google Scholar 

  • Li X, Ao Z, Liu J, Sun H, Rykov AI, Wang J (2016) Topotactic transformation of metal–organic frameworks to graphene-encapsulated transition-metal nitrides as efficient Fenton-like catalysts. ACS Nano 10:11532–11540

    Article  CAS  Google Scholar 

  • Li J-J, Weng B, Cai S-C, Chen J, Jia H-P, Xu Y-J (2018a) Efficient promotion of charge transfer and separation in hydrogenated TiO2/WO3 with rich surface-oxygen-vacancies for photodecomposition of gaseous toluene. J Hazard Mater 342:661–669

    Article  CAS  Google Scholar 

  • Li X, Huang X, Xi S, Miao S, Ding J, Cai W, Liu S, Yang X, Yang H, Gao J (2018b) Single cobalt atoms anchored on porous N-doped graphene with dual reaction sites for efficient Fenton-like catalysis. J Am Chem Soc 140:12469–12475

    Article  CAS  Google Scholar 

  • Liu P, Yang S, Zhang B, Yang H (2016) Defect-rich ultrathin cobalt–iron layered double hydroxide for electrochemical overall water splitting. ACS Appl Mater Interfaces 8:34474–34481

    Article  CAS  Google Scholar 

  • Liu H, Wang Y, Lu X, Hu Y, Zhu G, Chen R, Ma L, Zhu H, Tie Z, Liu J (2017) The effects of Al substitution and partial dissolution on ultrathin NiFeAl trinary layered double hydroxide nanosheets for oxygen evolution reaction in alkaline solution. Nano Energy 35:350–357

    Article  CAS  Google Scholar 

  • Liu L, Liu Q, Wang Y, Huang J, Wang W, Duan L, Yang X, Yu X, Han X, Liu N (2019a) Nonradical activation of peroxydisulfate promoted by oxygen vacancy-laden NiO for catalytic phenol oxidative polymerization. Appl Catal B 254:166–173

    Article  CAS  Google Scholar 

  • Liu L, Wang Y, Liu Q, Wang W, Duan L, Yang X, Yi S, Xue X, Zhang J (2019b) Activating peroxydisulfate by morphology-dependent NiO catalysts: structural origin of different catalytic properties. Appl Catalysis B 256:117806

    Article  CAS  Google Scholar 

  • Miranda LD, Bellato CR, Fontes MP, de Almeida MF, Milagres JL, Minim L (2014) Preparation and evaluation of hydrotalcite-iron oxide magnetic organocomposite intercalated with surfactants for cationic methylene blue dye removal. Chem Eng J 254:88–97

    Article  CAS  Google Scholar 

  • Nandan B, Bhatnagar M, Kashyap SC (2019) Cation distribution in nanocrystalline cobalt substituted nickel ferrites: X-ray diffraction and Raman spectroscopic investigations. J Phys Chem Solids 129:298–306

    Article  CAS  Google Scholar 

  • Song H, Zhang C, Liu Y, Liu C, Nan X, Cao G (2015) Facile synthesis of mesoporous V2O5 nanosheets with superior rate capability and excellent cycling stability for lithium ion batteries. J Power Sources 294:1–7

    Article  CAS  Google Scholar 

  • Strasser P, Gliech M, Kuehl S, Moeller T (2018) Electrochemical processes on solid shaped nanoparticles with defined facets. Chem Soc Rev 47:715–735

    Article  CAS  Google Scholar 

  • Sun Y, Gao S, Lei F, Xie Y (2015) Atomically-thin two-dimensional sheets for understanding active sites in catalysis. Chem Soc Rev 44:623–636

    Article  CAS  Google Scholar 

  • Taniguchi T, Watanabe T, Sugiyama N, Subramani A, Wagata H, Matsushita N, Yoshimura M (2009) Identifying defects in ceria-based nanocrystals by UV resonance Raman spectroscopy. J Phys Chem C 113:19789–19793

    Article  CAS  Google Scholar 

  • Wang Q, Chen L, Guan S, Zhang X, Wang B, Cao X, Yu Z, He Y, Evans DG, Feng J (2018a) Ultrathin and vacancy-rich CoAl-layered double hydroxide/graphite oxide catalysts: promotional effect of cobalt vacancies and oxygen vacancies in alcohol oxidation. ACS Catal 8:3104–3115

    Article  CAS  Google Scholar 

  • Wang Q, Wang X, Tian BJWS, Technology, (2018b) Catalytic performances of Ni/Fe layered double hydroxides fabricated via different methods in Fenton-like processes. Water Sci Technol 77:2772–2780

    CAS  Google Scholar 

  • Wang R, Yu Y, Zhang R, Ren X, Guo W (2022) Vacancy-rich structure inducing efficient persulfate activation for tetracycline degradation over Ni-Fe layered double hydroxide nanosheets. Sep Purif Technol 289:120663

  • Wang X, Spörer Y, Leuteritz A, Kuehnert I, Wagenknecht U, Heinrich G, Wang D (2015) Comparative study of the synergistic effect of binary and ternary LDH with intumescent flame retardant on the properties of polypropylene composites. RSC Adv 5:78979–78985

    Article  CAS  Google Scholar 

  • Wang Y, Liu D, Liu Z, Xie C, Huo J, Wang S (2016) Porous cobalt–iron nitride nanowires as excellent bifunctional electrocatalysts for overall water splitting. Chem Commun 52:12614–12617

    Article  CAS  Google Scholar 

  • Wu L, Hong J, Zhang Q, Chen B-Y, Wang J, Dong Z (2020) Deciphering highly resistant characteristics to different pHs of oxygen vacancy-rich Fe2Co1-LDH/PS system for bisphenol A degradation. Chem Eng J 385:123620

    Article  CAS  Google Scholar 

  • Xu W, Xue W, Huang H, Wang J, Zhong C, Mei D (2021) Morphology controlled synthesis of α-Fe2O3-x with benzimidazole-modified Fe-MOFs for enhanced photo-Fenton-like catalysis. Appl Catal B 291:120129

  • Zhang T, Chen Y, Wang Y, Le Roux J, Yang Y, Croue J-P (2014) Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation technology. Environ Sci Technol 48:5868–5875

    Article  CAS  Google Scholar 

  • Zhang N, Li X, Ye H, Chen S, Ju H, Liu D, Lin Y, Ye W, Wang C, Xu Q (2016) Oxide defect engineering enables to couple solar energy into oxygen activation. J Am Chem Soc 138:8928–8935

    Article  CAS  Google Scholar 

  • Zhang Y, Xie W, Ma J, Chen L, Chen C, Zhang X, Shao M (2021) Active facet determination of layered double hydroxide for oxygen evolution reaction. J Energy Chem 60:127–134

    Article  CAS  Google Scholar 

  • Zhuang L, Ge L, Yang Y, Li M, Jia Y, Yao X, Zhu Z (2017) Ultrathin iron-cobalt oxide nanosheets with abundant oxygen vacancies for the oxygen evolution reaction. Adv Mater 29:1606793

    Article  Google Scholar 

  • Zubair M, Daud M, McKay G, Shehzad F, Al-Harthi MA (2017) Recent progress in layered double hydroxides (LDH)-containing hybrids as adsorbents for water remediation. Appl Clay Sci 143:279–292

    Article  CAS  Google Scholar 

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Funding

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 41877132 and 51908242), Shandong Provincial Natural Science Foundation of China (Grant No. ZR2020KB009), and Science and Technology Program of University of Jinan (Grant No. XKY1918).

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Authors and Affiliations

  1. School of Water Conservancy and Environment, University of Jinan, Jinan, 250022, China

    Rongyao Wang, Yanjun Yu, Ruijuan Zhang, Xiaohua Ren & Weilin Guo

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  1. Rongyao Wang
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  2. Yanjun Yu
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  3. Ruijuan Zhang
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  4. Xiaohua Ren
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  5. Weilin Guo
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Contributions

Rongyao Wang analyzed and interpreted the data and was a major contributor in writing the manuscript. Yanjun Yu performed formal analysis; writing—review and editing; and supervision. Rruijuan Zhang performed investigation and formal analysis. Xiaohua Ren performed visualization, supervision, validation, and formal analysis. Weilin Guo performed supervision; conceptualization; resources; writing—reviewing and editing; project administration; and funding acquisition. All authors read and approved the final manuscript.

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Correspondence to Weilin Guo.

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Wang, R., Yu, Y., Zhang, R. et al. Elucidating the origin mechanism of a morphology-dependent layered double hydroxide catalyst toward organic contaminant oxidation via persulfate activation. Environ Sci Pollut Res 29, 79126–79139 (2022). https://doi.org/10.1007/s11356-022-21347-y

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