Smart Poly(N-Isopropylacrylamide)-Based Microgels Supplemented with Nanomaterials for Catalytic Reduction Reactions—A Review
Abstract
:1. Introduction
2. Fundamentals of HMGs for CRRs
2.1. Synthesis of Hybrid Microgels
2.1.1. Synthesis of Microgels in HMGs
2.1.2. Synthesis of NMs in HMGs
- Upon the dissolution of the precursor salt () in an aqueous medium, the salt is dissociated into ions (Equation (1)).
- These metal ions are then reduced (the species is capable of giving electrons to the interacting molecule) into zero-valent metal atoms () (Equation (2)).
- Almost 30 metal atoms combine to give NMs.
- In the absence of any stabilization medium, the NMs undergo aggregation due to higher surface energy values.
- The presence of the stabilization medium/surfactant confines the fabricated materials in the nano range (Equation (3)).
2.1.3. Synthesis of Microgels in HMGs
In Situ Generation of NMs within Microgels
Microgels Grown on Pre-Synthesized NMs Core
2.2. Characterization Techniques for HMGs
2.3. Properties of HMGs
2.3.1. Temperature Responsiveness of HMGs
2.3.2. pH Responsiveness of HMGs
2.3.3. Optical Responsiveness of HMGs
3. Fundamentals of CRRs in HMG
3.1. Main Process and Progress Detection
- HMGs are first placed in the swelled state to overcome any possible diffusional barrier that can be observed by the pollutant in reaching the NPs present in the HMGs.
- The pollutant then becomes physically adsorbed on the surface of the NPs present in the HMGs.
- The reducing agent either becomes absorbed on the surface of NPs (by the Langmuir–Hinshelwood (LH) mechanism), or remains present in the solution (by the Eley–Rideal (ER) mechanism) during this process.
- The reductant provides the electron to the pollutant by utilizing the electron transferring/transducing surface of the NPs present in the HMGs, and the pollutant is reduced.
- The formed reduced product is then desorbed from the surface of the NPs and is diffused out of the HMGs into the solution.
3.2. Kinetics and Thermodynamics
3.3. Mechanism
4. Literature Survey/Recent Advancements
4.1. Advancements in Terms of Morphology
4.1.1. Homogenous HMGs
4.1.2. Heterogeneous HMGs
Rigid Core@Polymeric Shell/NM-Based HMGs
Polymeric Core@Polymeric Shell/NM-Based HMGs
4.2. Advancements in Terms of NMs in HMGs
4.2.1. Monometallic NM-Based HMGs
4.2.2. Bimetallic/Muli-Metallic NM-Based HMGs
4.2.3. Nanocomposites (NCs) Based HMGs
Catalytic Assembly | Type of HMGs | Pollutant | Pollutant Dose | Catalyst Dose | Reductant Dose | Rate Constant | Reduction Time | Percentage Reduction | Ref. |
---|---|---|---|---|---|---|---|---|---|
Thiol-functionalized PNIPAM-AAc/Cu NPs | Monometallic | 4NP | 0.1 mM (1 mL) | 0.06 mg/mL (0.2 mL) | 10 mM (1 mL) NaBH4 | 0.0223 min−1 | 18 min | 100% | [67] |
Thiol-functionalized PNIPAM-AAc/(Cu/Pd NPs) | Bimetallic | 0.223 min−1 | 120 s | 100% | |||||
Thiol-functionalized PNIPAM-AAc/Cu NPs | Monometallic | MB | 0.1 mM (1 mL) | 0.06 mg/mL (0.2 mL) | 10 mM (1 mL) NaBH4 | -- | 24 min | 100% | |
Thiol-functionalized PNIPAM-AAc/(Cu/Pd NPs) | Bimetallic | 0.173 min−1 | 165 s | 100% | |||||
PNIPMAM-MAC/(Ag/Ni NPs) | Bimetallic | MO | 0.80 mM | 85.71 g/mL | 9.65 mM NaBH4 | 0.925 min−1 | 10 min | 100% | [57] |
MR | 0.525 min−1 | 9 min | 100% | ||||||
EBT | 0.540 min−1 | 9 min | 100% | ||||||
CR | 0.486 min−1 | 10 min | 100% | ||||||
PNIPAM-MAC/Zr NPs@GS | NCs | 4NP | 0.085 mM | 0.2 mL | 0.1 g NaBH4 | 0.010 min−1 | 68 min | 36% | [5] |
SN | 0.012 min−1 | 82 min | 41.8% | ||||||
CR | 0.015 min−1 | 50 min | 48.6% | ||||||
4NAs | 0.0210 min−1 | 42 min | 70% | ||||||
DNPO | 0.023 min−1 | 44 min | 60% | ||||||
4NBA | 0.010 min−1 | 48 min | 72% | ||||||
CNTs@PNIPAM-VBDB@Pd NPs | NCs | NB | 1 mM | 0.01 g | 1 bar H2 gas at 40 | -- | 120 min | 98% | [70] |
TA-HNTs@PNIPAM/AuNPs | NCs | 4NP | 1 mM (75 L) | 0.05 mL | 133 mM (0.5 mL) NaBH4 | 0.345 min−1 | 10 min | 100% | [71] |
Perlite glass@PNIPAM-AAm@Pd/NPs | NCs | NB | 1 mM | 0.03 g | 1 atm H2 gas at 40 | -- | 90 min | 98% | [72] |
5. Conclusions
6. Future Perspectives
- Thermodynamic parameters should be given as much significance as kinetic analysis because thermodynamic studies provide critical insights regarding underlying reactions.
- There is a recent trend in the use of the response surface methodology (RSM) as a means for the optimization of the catalytic reactions [73]. RSM is an advanced computational and statistical tool that includes the interaction coefficients in the modeling of the underlying reaction [74]. To the best of our knowledge, this approach has not yet been implemented for MGs or HMGs, making it one of the prospective fields for exploration.
- The implementation of the RSM approach for photocatalytic reactions is just starting to be documented [35], indicating that this field should be implemented for catalytic reduction-based reactions as well.
- Data-driven approaches, particularly machine learning, are also finding use in almost every research domain [75]. These approaches can be implemented for the modeling of HMGs for CRRs as well.
- The use of novel types of nanocomposite materials, comonomers, or inorganic substances can develop appropriate and novel nanocatalysts.
- The morphological features of HMGs can be used as a key switch in wastewater treatment plants for simultaneous biomedical (antibacterial, antifungal, antioxidant activities, etc.) and CRR reactions.
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Abbreviations
DPE | 1:1-Diphenylethane |
1B2NB | 1-bromo-2-nitrobenzene |
1B3NB | 1-bromo-3-nitrobenzene |
1C2NB | 1-chloro-2-nitrobenzene |
1C4NB | 1-chloro-4-nitrobenzene |
CEB | 1-chloro-4-ethylbenzene |
1M2NB | 1-methyl-2-nitrobenzene |
1M22DNB | 1-methyl-2,2-dinitrobenzene |
1M24DNB | 1-methyl-2,4-dinitrobenzene |
VIM | 1-vinylimidazole |
VBDB | 1-vinyl-3-butylimidazolium bromide |
24Dc1NB | 2,4-dichloro-1-nitrobenzene |
DNPO | 2,4-Dinitrophenol |
AMPS | 2-acrylamido-2-methylpropane sulfate |
AMPSA | 2-acrylamido-2-methyl-propane sulfonic acid |
HMABP | 2-hydroxy-4-(methacryloyloxy)-benzophenone |
2MO4NA | 2-methoxy-4-nitroaniline |
2NA | 2-nitroaniline |
2NPM | (2-nitrophenyl) methanol |
3MSi | 3-methacryloxypropyltrimethoxysilane |
3MO4NA | 3-methoxy-4-nitroaniline |
4CANI | 4-chloroaniline |
4NA | 4-nitroaniline |
4C12DNB | 4-chloro-1,2-dinitrobenzene |
4B4NB | 4-Bromo-4-nitrobenzene |
4NAs | 4-nitroanisole |
4NBA | 4-nitrobenzoic acid |
4NP | 4-nitrophenol |
5NB13DA | 5-nitrobenzene-1,3-diamine |
AA | Acrylamide |
AAc | Acrylic acid |
AAm | Allylamine |
ANI | Aniline |
AB | Azobenzene |
BCH | Bicyclo[2.2.1]heptane |
CNTs | Carbon nanotubes |
CRR | Catalytic reduction reaction |
CFI | Confocal imaging |
CR | Congo red |
COP | Copolymerized |
CV | Crystal violet |
CD | Cyclodextrin |
DSPB | Diblock spherical polymer brushes |
DEAEMA | Diethylaminoethyl methacrylate |
DSC | Differential scanning calorimetry |
DHC | Dihydrochalcone |
DLS | Dynamic light scattering |
EDX | Energy-dispersive X-ray spectrometer |
EY | Eosin Y |
EBT | Eriochrome Black T |
EDTA | Ethylenediaminetetraacetic acid |
EB | Ethylbenzene |
FTIR | Fourier transform infrared spectroscopy |
FEPol | Free-radical emulsion polymerization |
Au | Gold |
GO | Graphene oxide |
GS | Graphene sheets |
t1/2 | Half-life time |
HMGs | Hybrid microgels |
HEMA | Hydroxyethyl methylacrylate |
ICP | Inductively coupled plasma |
Fe3O4 | Iron oxide |
MG | Malachite green |
MS | Mass spectrometry |
MAC | Methacrylic acid |
MB | Methylene blue |
MO | Methyl orange |
MR | Methyl red |
DM4NA | N,N-dimethyl-4-nitroaniline |
NCs | Nanocomposites |
NMs | Nanomaterials |
NPs | Nanoparticles |
NRs | Nanorods |
Ni | Nickel |
NB | Nitrobenzene |
NMR | Nuclear magnetic resonance |
OVAT | One-variable-at-a-time |
TOL | p-Toluidine |
Pd | Palladium |
PIMP | Photoiniferter-mediated polymerization |
Pt | Platinum |
PAMP | Poly (2-acrylamide-2-methylpropanesulfonic acid) |
PMETAC | Poly 2-(methacryloyloxy)ethyl-trimethyl-ammonium chloride |
PNIPAM | Poly (N-isopropyl acrylamide) |
Bpnipam | Poly (N-isopropylacrylamide) brushes |
PNIPMAM | Poly (N-isopropyl methacrylic acid) |
PS | Polystyrene |
PSV | Polystyrene coated with 4-vinylbenzyl N,N-diethyldithiocarbamate |
PSS | Polystyrene sulfonate |
PFO | Pseudo-first-order kinetics |
RB5 | Reactive black 5 |
SN | Safranin |
SEM | Scanning electron microscopy |
SiO2 | Silica |
Ag | Silver |
NaBH4 | Sodium borohydride |
SPR | Surface plasmonic resonance |
TA-HNTs | Tannin-aminopropyltriethoxysilane-coated halloysite nanotubes |
TEOS | Tetraethoxysilane |
TGA | Thermal gravimetric analysis |
TChPILs | Thiol-functionalized chitosan poly(protic ionic liquids) |
TEM | Transmission electron microscopy |
TOF | Turnover frequency |
UV–VIS | Ultraviolet–visible spectroscopy |
VPTT | Volume phase transition temperature |
XRD | X-ray Diffraction |
XPS | X-ray photoelectron spectroscopy |
Zr | Zirconium |
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HMGs | Techniques Used | Main Technique Discussed | Purpose/Advantage | Ref. |
---|---|---|---|---|
PNIPAM-AAc/Ag NPs | FTIR UV–VIS TEM | FTIR | To study the chemical functionalities of microgels To validate the formation of microgels To study the chemical interactions of NMs with HMGs To study the orientations/conformations of polymeric chains of HMGs | [9] |
PNIPAM-MAC/CuO NPs | SEM XRD FTIR UV–VIS | SEM | To estimate any variation in surface characteristics upon incorporation of NMs within microgels To study any fracture and failure mechanics of the synthesized HMGs To investigate the surface morphology of HMGs To affirm the incorporation of NMs in the microgels in | [7] |
PNIPAM-AMPS/Cu NPs HMGs and PNIPAM-AMPS/Ni NPs | EDX FTIR TGA TEM UV–VIS | EDX | Elemental composition of HMGs is investigated via EDX Purity of HMGs Percentage composition of the elements Detection of the impurities present in HMGs | [27] |
PNIPAM/Ag NPs | TEM FTIR UV–VIS | TEM | To investigate the structural properties of dispersed phases To develop micrographs of HMGs for identifying the NMs present at the localized regions Study of phase morphology Investigation of the size of NPs Estimation of the size distribution of NPs in HMGs Comparison of particle sizes of HMGs | [20] |
PNIPAM-MAC/Au NPs | XRD ICP-MS SEM TEM TGA UV–VIS | XRD | To examine the existence of crystalline structure in microgels and loaded NPs To study the purity of NPs added to microgels To study the diffraction planes associated with the NMs in HMGs To investigate percentage crystallinity in HMGs To estimate the size of the NPs in HMGs | [12] |
Ni-doped Fe3O4 NPs@PNIPAM | XPS XRD UV–VIS DLS | XPS | To study the NP interaction with different groups of microgels To estimate the stability of NPs To study the vacancies generated by the dopant in HMGs To study the concentration of NMs in HMGs | [28] |
PS@PNIPAM-MAC/Ag NPs | TGA FTIR TEM DLS UV–VIS | TGA | To determine the successful fabrication of NPs in HMGs Thermal stability of microgels and HMGs is investigated by TGA | [17] |
PNIPAM-AMPS/Ag NPs | DLS FTIR XRD TGA UV–VIS | DLS | Investigating the changes in particle size of the microgels due to uploaded NP contents and temperature variations Swelling/de-swelling characteristics of HMGs To study the morphological transitions of HMGs | [8] |
PNIPAM-AMPS/Co NPs | UV–VIS FTIR TEM DLS XRD EDX | UV–VIS | To study the successful fabrication of NMs in microgels by characteristics of SPR To study the stability of the HPAs To study any size changes in NMs in HPAs by variation in SPR peaks To analyze the impact of swelling/de-swelling of hybrid microgels based on their optical and plasmonic characteristics | [29] |
PNIPAM/Ag NPs | ICP-MS DLS DSC SEM TEM CFI | ICP-MS | To study the content/mass of the NMs present in the HMGs | [30] |
PNIPAM/Ag NPs and PNIPAM/Au NRs | DSC DLS TEM FTIR | DSC | To study the conformational changes in the HMGs To investigate the impact of thermal changes on HMGs To study the VPTT temperature of gels and HMGs | [31] |
Catalytic Assembly
| Morphology Type Salient Characters | Synthesis: Total Steps | Pollutant | Catalytic Reduction
| Observed Parameters
| Kinetics Studies | Remarks | Ref. |
---|---|---|---|---|---|---|---|---|
| Homogenous COP | Two steps:
| 4NP |
|
| PFO | The detailed impact of the temperature effect on rate constants was studied. Moreover, the VPTT-based modulation of the catalytic activity was carried out. | [34] |
| Homogenous CoP | Two steps:
| 4NP |
|
| PFO | ||
| Homogenous Metallic assembly | Three steps:
| 4NP |
|
| PFO | The author studied the thermodynamic parameters of Ea, , and using the Eyring equation for the 4NP degradation reaction. The authors affirm the need for the catalyst to carry out this reduction reaction based on the kinetic and thermal barrier of the reaction. | [42] |
MO CR EBT |
| MO
| PFO | |||||
Single layered Assembly
| Homogenous COP | Single layered Assembly Two steps:
| CR |
|
| PFO | The authors studied thermodynamic parameters associated with the reaction via Eyring equation. The doubling of the shells hindered the reduction capabilities of assemblies, indicating that the diffusional barrier faced by reactants is the significant parameter for controlling efficacy. | [43] |
Double layered assembly
| Double layered Assembly Three steps:
|
| ||||||
| Homogenous COP | Two steps:
| 4NP 4NAs DNP MR RB5 MG MO EBT |
| 4NP
| PFO | The authors utilized the combination of organic (PNIPAM-AAc) and inorganic (GO) materials as a fabrication of the Ag NPs. The authors figured out that for most of the studied pollutants, the combination of organic and inorganic materials exhibited better results in terms of catalytic efficacy in comparison to the organic microgels. GO facilitated the catalytic reduction process by providing synergistic effects for the transduction of the electron between the reductant and the reactant. Consequently, high reduction rates were documented for the assembly containing GO alongside the hybrid microgels. | [44] |
| Heterogeneous Layered | Three steps:
| 4NP
| |||||
| Homogenous COP | Two steps:
| 4NP 2NP 2NA MO MB EY | 4NP
| 4NP
| PFO | The thermodynamic parameters were also investigated alongside the kinetic parameters for the catalytic reduction reactions. It was observed that the rate constant values of these reactions were found to be increasing with increments in the temperature parameter value. | [8] |
| Homogenous COP | Two steps:
| RhB 4NP | RhB
| RhB
| PFO | An excellent comparative study was performed by carrying out the reduction for two different NPs under the same conditions of catalytic reduction. Pd NP-based HMGs exhibited better results in comparison to the Ag NP-based HMGs. To obtain further insights into reduction reaction, surface-area-based normalized rate constants were investigated in the study as well. | [4] |
| Homogenous COP | Two steps:
| RhB
| PFO | ||||
| Homogenous COP | Two steps:
| 3NP 4NP 4NAs 4NBA DNP CR CV MB MR RB5 |
| 3NP
| PFO | Excellent comparative studies were performed where the comparison of %R can be carried out among different pollutants as the CRRs were carried out under similar conditions. The authors identified the factors of the chemical structure of pollutants, presence of bulky groups, steric hindrance, and orientation of NPs as the crucial factors influencing the %R. | [45] |
| Homogenous COP | Two steps:
| MO |
|
| PFO | The recycling experiments and FTIR-based analysis of the synthesized catalyst were carried out for efficient investigation. | [7] |
| Homogenous COP | Two steps
| MG |
|
| PFO | Numerous parameters, including catalyst dose, reducing agent dose, and MG dose, were optimized using the OVAT kinetic approach. | [9] |
Catalytic Assembly
| Morphology Type Salient Characters | Synthesis: Total Steps | Pollutant | Catalytic Reduction
| Observed Parameters
| Kinetics Studies | Remarks | Ref. |
---|---|---|---|---|---|---|---|---|
| Heterogeneous core@shell CoP | Three steps:
| EY |
|
| PFO | Detailed kinetic study documenting the impact of [catalyst], [pollutant], and [NaBH4] on rate constant was thoroughly investigated. | [50] |
MB |
|
| PFO | |||||
| Heterogeneous core@ grafted shell supplied with NPs | Three steps:
| CEB EB BCH DPE DHC ANI CANI TOL |
| CEB
| -- | TOF was investigated for the catalysts. Short reaction time was observed for sterically less hindered pollutants, while deactivation of electron-deficient DHC exhibited a longer time.In the case of nitroarenes, the presence of chlorine and alkyl branches does not influence the TOF of these pollutants as such. | [55] |
| Heterogeneous Core@grafted shell supplied with NPs | Four steps:
| 4NP |
|
| PFO | Surface-initiated PIMP methodology was utilized that was effective in the fabrication of grafted morphology of these catalytic assemblies. The interactions (hydrogen bonding and hydrophobic interactions) developed by the assembly with the dye were found to modulate the rate of the reaction. | [56] |
| Heterogeneous Core@grafted shell supplied with NPs | Four steps:
| 4NP |
|
| PFO | ||
| Heterogeneous core@shell CoP Bimetallic assembly | Two steps:
| MO CR EBT MR |
| MO
| PFO | The mechanism associated with the underlying reaction was found to be the Langmuir–Hinshelwood mechanism. | [57] |
| Heterogeneous Core@shell@shell Surface-deposited Au NPs | Five steps:
| 4B4NB 1B2NB 1B3NB 1C4NB 1C2NB 24Dc1NB 4C12DNB 2NPM 4NA 2NA 5NB13DA 2MO4NA 3MO4NA DM4NA 1M2NB 1M22DNB 1M24DNB |
| 4B4NB
| -- | An excellent study documenting the variety of nitroarene pollutants was documented. The catalyst exhibited catalytic efficacy in the range of 45% to 95%. Depending upon the difficulty of the degradation, a variety of reaction times were observed. Moreover, the impact of swelling/de-swelling properties of the PNIPAM was utilized to modulate the rate of the reduction reaction. The reusability studies exhibited that the catalyst exhibited 95% reduction efficacy even after eight cycles of usage. The authors also studied the leaching effects of the Au NPs from the assembly, indicating that the synthesized catalyst possessed excellent capability for the effective fabrication of Au NPs. | [58] |
| Heterogeneous core@shell DSPB assembly | Four steps:
| 4NPNB |
| At 25 °C 4NP
4NP
| PFO | Competitive reduction of both pollutants was carried out, and it was observed that the catalyst retains its selective reduction capabilities even during the simultaneous reduction of pollutants. The catalyst effectively degraded 4NP better in comparison to NB at a lower temperature, while the opposite trend was indicated for higher temperatures. | [59] |
| Heterogeneous Layered reactors | Four steps:
| DNPO |
|
| -- | The layered-designed catalytic reactor was developed, and it was identified that PNIPAM acted as a switch for improving/decreasing the catalytic efficacy of the reactor. | [60] |
| Heterogeneous Core@grafted shell | Three steps:
| 4NP |
|
| PFO | The authors elucidated that the polymeric materials selected for the formation of assembly are essential for the acquisition of high catalytic efficacy. The catalytic efficacy observed in the case of AB-PNIPAM was found to be less in comparison to the PNIPAM grafted assembly. | [32] |
| Three steps:
|
| ||||||
| Heterogeneous core@shell COP | Three steps:
| 4NP |
|
| PFO | Thermodynamic studies based on the Eyring equation were carried out for CRR of the 4NP via using the synthesized HMGs. The impact of VPTT was also investigated on the catalytic efficacy of these HMGs. | [61] |
| Heterogeneous core@shell COP | Three steps:
| 4NP |
|
| PFO | The recyclability studies revealed that the synthesized HMGs were quite effective for three usage cycles in terms of . | [21] |
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Alam, M.W. Smart Poly(N-Isopropylacrylamide)-Based Microgels Supplemented with Nanomaterials for Catalytic Reduction Reactions—A Review. ChemEngineering 2023, 7, 105. https://doi.org/10.3390/chemengineering7060105
Alam MW. Smart Poly(N-Isopropylacrylamide)-Based Microgels Supplemented with Nanomaterials for Catalytic Reduction Reactions—A Review. ChemEngineering. 2023; 7(6):105. https://doi.org/10.3390/chemengineering7060105
Chicago/Turabian StyleAlam, Mir Waqas. 2023. "Smart Poly(N-Isopropylacrylamide)-Based Microgels Supplemented with Nanomaterials for Catalytic Reduction Reactions—A Review" ChemEngineering 7, no. 6: 105. https://doi.org/10.3390/chemengineering7060105