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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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Front. Environ. Sci. Eng.    2024, Vol. 18 Issue (12) : 151    https://doi.org/10.1007/s11783-024-1911-5
Advances in bimetallic metal organic frameworks (BMOFs) based photocatalytic materials for energy production and waste water treatment
Pankaj Sharma1,3, Amit Kumar1,2(), Tongtong Wang2(), Mika Sillanpää4, Gaurav Sharma1, Pooja Dhiman1
1. International Research Centre of Nanotechnology for Himalayan Sustainability (IRCNHS), Shoolini University, Solan 173229, India
2. Institute for Interdisciplinary and Innovate Research, Xi’an University of Architecture and Technology, Xi’an 710055, China
3. School of Physics & Materials Science, Shoolini University, Solan 173229, India
4. Department of Biological and Chemical Engineering, Aarhus University, Aarhus 8000, Denmark
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Abstract

● BMOFs offer high conductivity, active sites, and photo-responsiveness.

● BMOFs have adjustable active sites for high photocatalytic activity.

● Various tailoring strategies for improving BMOFs properties were summarized.

● Advances in BMOFs materials for photocatalytic applications are discussed.

● BMOFs are integrated to form Z and S-scheme heterojunctions.

Photocatalysis contributes significantly to global economic development and has promising environment application like degradation of organic contamination and energy production. The initiatives are concentrated on accelerating the reaction rates and designing novel photocatalysts for improving the ability and enhance the selectivity toward specific products. Recently, bimetallic nanoparticles (NP)/metal-organic frameworks (BMOFs), gained broader interests in heterogeneous catalysis due to their unique photocatalytic properties. Coupling of bimetallic nanoparticles with metal-organic frameworks has found to be a highly effective strategy to improve the photocatalytic activity and broaden the reaction scope. In addition, BMOFs have been found to have exceptional capabilities in breaking down organic pollutants, reducing heavy metals and producing energy. These remarkable abilities are believed to be a result of the combined effects of the bimetallic centers. This review summarizes and analyses the recent advancements in BMOFs based materials especially heterojunctions for degradation of organic pollutants and also in energy production. Different synthesis techniques of designing BMOFs composites are highlighted in this study. The underlying mechanism synergistically enhanced performance in heterogeneous catalysis is thoroughly examined. This review also explores the challenges and possible future pathways in photocatalysis using BMOFs. There are several important challenges that need to be addressed in order to improve the durability of BMOFs in real-world conditions, optimize the synthesis process for industrial applications and gain a deeper understanding of the complicated structures that influence their photocatalytic processes.
Keywords Metal organic frameworks      Heterojunctions      Photocatalysis      Bimetallic      Energy production      Water treatment     
Corresponding Author(s): Amit Kumar,Tongtong Wang   
Issue Date: 15 October 2024
 Cite this article:   
Pooja Dhiman,Gaurav Sharma,Mika Sillanpää, et al. Advances in bimetallic metal organic frameworks (BMOFs) based photocatalytic materials for energy production and waste water treatment[J]. Front. Environ. Sci. Eng., 2024, 18(12): 151.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-024-1911-5
https://academic.hep.com.cn/fese/EN/Y2024/V18/I12/151
Fig.1  BMOFs as photocatalysts for environmental application, various photocatalytic properties of BMOFs and synthetic strategies for constructing BMOF and their heterostructures with other semiconductors, BMOFs used as photocatalyst for energy production and organic pollutant reduction.
Fig.2  (a) Photocatalytic organic pollutant degradation mechanism, (b) photocatalytic hydrogen evolution mechanism, (c) photocatalytic CO2 reduction mechanism.
Fig.3  (a) Charge transfer mechanism in Schottky junction, (b) Charge transfer mechanism convention Z-scheme heterostructures, (c) Charge transfer mechanism in S-scheme heterojunction.
Fig.4  (a) Solvothermal synthesis of CdS NPs decorated Fe/Mn-MOF, (b) average particle size distribution of CdS/FeMn-MOF, (c) SEM picture of Fe/Mn-MOF, (d) SEM image of CdS NPs decorated Fe/Mn-MOF, (e) HRTEM image of 10%FeMn-MOF/CdS, Reprinted from Zhang et al. (2024) with permission from Elsevier; (f) construction of FeCu-BDC bimetallic MOF, (g) SEM image of FeCu- BDC bimetallic MOFs, (h) elemental mapping of FeCu-BDC bimetallic MOFs, Reprinted from Tong et al. (2024) with permission from Elsevier.
Fig.5  (a) Synthesis of bimetallic (Zn/Co)2(blm)4 bimetallic MOF through vapor transformation technique, Reprinted from Ma et al. (2022) with permission from Elsevier; (b) schematic fabrication of Cu-ZIF-67, Reprinted from Guo et al. (2024) with permission from Elsevier.
Fig.6  Advantages of BMOFs over other photocatalysts.
Fig.7  (a) Photocurrent response of Zn/Co –ZIF MOF, (b) MB degradation efficiency over Zn/Co (1:1)-ZIF, (c) degradation percentage of different pollutants by Zn/Co (1:1)-ZIF, Reprinted from Zhu et al. (2023) with permission from Elsevier; (d) degradation of NOR by Fe/Ti-MOFs (1.5:1), (e) degradation pathway of NOR during photocatalytic process, (f) photocatalytic mechanism of NOR degradation using bimetallic Fe/Ti-MOFs (1.5:1) under visible light, Reprinted from Gao et al. (2023a) with permission from Elsevier; (g) efficiency of reducing Cr(VI) in the presence of NH2-MIL-125 (Ti/Ce) and NH2-MIL-125 (Ti), (h) photocatalytic mechanism for the Cr(VI) reduction by NH2-MIL-125 (Ti/Ce) photocatalyst, Reprinted from Meng et al. (2023) with permission from Elsevier.
No. Photocatalysts Photocatalysts dosage Fabrication method Pollutant/conc. Solution pH Light source/intensity performance Ref.
1 Zr/Cu-MOFs 40 mg Precipitation refluxing method TC, 20 mg/L 7 UV light 95% degradation in 80 min Kaushal et al. (2022)
2 Ti-In MOF 5 mg Solvothermal BPA, 50 mg/L 7 Xe lamp, 300 W 80% removal in 80 min Li et al. (2022a)
3 Zn-Zr MOFs 0.9 g/L One pot hydrothermal RhB, 40 mg/L – Xe lamp, 300 W 98.1% degradation in 60 min Zhang et al. (2022b)
4 CuFe2O4@MIL-100(Cu, Fe) 5 mg Hydrothermal MB, 50 ppm 1 Xe lamp, 300 W 95% in 40 min Shi et al. (2021)
5 FeNi-MOF 80 mg/L Solvothermal ENR, 30 mg/L 11 – 95% in 40 min Aldhalmi et al. (2023)
6 Fe/Mn-MOF@CdS 20 mg Self-assembly TC, 20 mg/L 5 Xe lamp, 300 W 90.95% in 160 min Zhang et al. (2024)
7 GCN/Mn-Fe-BTC 0.5 g/L Microwave assisted hydrothermal RR-195, 20 mg/L 3 Sunlight 100% in 30 min Nguyen et al. (2024)
8 Ag50-Zn50-BTC/GO Microwave assisted hydrothermal RY-145, 20 mg/L 3 Fluorescent lamp, 60 W 100% in 35 min Nguyen et al. (2021b)
9 Fe/Ti-MOF-NH2(3:1)/PS/vis 100 mg/L Solvothermal Orange II, 50 mg/L 5 Xe lamp, 300 W 100% in 10 min Wang et al. (2018a)
10 Ni/Fe-MOF 5 mg Microwave assisted solvothermal RhB, 3×10−5 mol/L 3 LED lamp, 40 W 96% in120 min Nguyen et al. (2021a)
11 Ti-Ni-MOF 10 mg One-step solvothermal TC – Xe lamp, 300 W 83% degradation in 60 min Zhao et al. (2024)
12 NH2-MIL-125(Ti/Ce) 2.0 mg Partial substitution Cr (VI), 50 mg/L 2 Mercury lamp 97% removal in 60 min Meng et al. (2023)
13 NH2-MIL-125(Ti/Zr) 250 mg/L Partial substitution Acetaminophen (ACE), 5 mg/L 7 Xe lamp, 600? W/m2 100% degradation in 180 min Gómez-Avilés et al. (2019)
14 Fe/Ce-MOFs 0.8 g DBD plasma MO, 20 mg/L – Xe lamp, 300 W 93% degradation in 30 min Tang et al. (2022)
15 Co-MIL-53(Fe)–NH2/UIO-66-NH2 10 mg Hydrothermal TC, 25 mg/LOTC, 25 mg/L 7 Xe lamp, 400? W/m2 96% and 83% degradation of TC and OTC in 16 min Ye et al. (2022)
16 MIL-53(Fe/Co)/CeO2, – Solvothermal Atrazine (ATZ), 10 mg/L 12 Visible light, 80 W 99.8% degradation in 60 min Roy et al. (2022)
17 BiOBr@ZnFe-MOF 15 mg One step solvothermal RhB, 5 mg/L – Xe lamp, 300 W 84.9% degradation in 90 min Shi et al. (2022)
18 Ti/Ni-MOL/In2Se3 10 mg – TC, 150 mg/L – Xe lamp 96.4% degradation in 90 min Li et al. (2022c)
Tab.1  Recent advances in bimetallic MOF based materials for photocatalytic pollutant degradation
Fig.8  (a, b) HER of synthesized NH2-MIL-125-Ni10%/Ti and pure NH2-MIL-125, NH2-MIL-125(Ti), (c) SVP spectra of NH2-MIL-125 Ni10%/Ti, Reprinted from Chang et al. (2022) with permission from Elsevier; (d) H2 production rate of In/Ni-MOF, In/In-MOF, In/Co-MOF, In/Fe-MOF and In/Mn-MOF, (e) photocatalytic H2 production mechanism over In/Ni-MOF, Reproduced Chen et al. (2024b) with permission from Elsevier; (f) N2 adsorption-desorption plots of various synthesized catalysts Zr(2.5%–10%)/Cu-H2BDC-BPD, (g) effect of EY concentration on hydrogen evolution, (h) effect of sacrificial agents on HER during photocatalysis, (i) photocatalytic hydrogen evolution mechanism over Zr/Cu-(H2BDC-BPD) photocatalyst, Reprinted from Yallur et al. (2023) with permission from Elsevier.
Fig.9  (a) LVS plots of H2ATA, Zr-ZTZ, Zr/Fe-ATA, Zr/Cu-ATA and Zr/Co-ATA, (b) photocatalytic HCOO− production rate of Zr/Cu-ATA, Reprinted from Ezugwu et al. (2023) with permission from Elsevier; (c) photocatalytic CO production rate of Fe-MOX, Ni/Fe-MOF, Co/Fe-MOF photocatalysts, (d, e) time-yield curves of (Co/Fe-MOF) and (Fe-MOF) and Ni/Fe-MOF for the total CO produced by photoreduction, (f) photocatalytic CO2 reduction mechanism of Co/Fe-MOF photocatalyst, Reprinted from Yang et al. (2023b) with permission from Elsevier.
AQY Apparent quantum efficiency
BET Brunauer-Emmett-Teller
BMOF Bimetallic metal organic frameworks
CB Conduction Band
CIP Ciprofloxacin
EDS Energy dispersive Spectra
EF Fermi energy
Eg Energy gap
eV Electron volt
e− Electrons
h Hour
h+ Holes
HER Hydrogen evolution rate
HUMO Highest occupied molecular orbit
LMCT Ligand to metal charge transfer
LUMO Lowest unoccupied molecular orbit
MB Methylene Blue
min Minutes
MMCT Metal to metal charge transfer
MO Methylene Orange
MOF Metallic organic frameworks
NOR Norfloxacin
NPs Nanoparticles
OP Oxidation Photocatalyst
OTC Oxytetracyclin
ROS Reactive oxygen species
RP Reduction Photocatalyst
SC Semiconductor
SEM Scanning electron microscopy
SHE Standard hydrogen electrode
TC Tetracycline
TEM Transmission electron microscopy
VB Valance band
  
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