Adsorption Of Catechol Research Articles

Exploring the adsorption of Catechol and Resorcinol onto Croton caudatus activated carbon: An integrated experimental and theoretical approach

The present work aimed to examine the process for adsorption of Catechol (CT) and Resorcinol (RS) onto activated carbon that was obtained from Croton caudatus biomass (CAB). Using a batch method, the maximum removal efficiencies of 99.23 % for CT and 98.68 % for RS was achieved at adsorbent dosage-0.2 g L-1, reaction time-60 min; concentration-100 mgL-1 CT and 80 mgL-1 RS; and pH 6.0 CT and pH 4.0 RS, respectively. A maximum equilibrium adsorption of 56.05 mgg-1 and 61.85 mgg-1 was achieved at pH 6.0 and pH 4.0 for CT and RS. The adsorption behavior of both adsorbates on activated carbon were best described by the Langmuir model (correlation coefficients (R2) = 0.996 for CT and 0.995 for RS) and the pseudo-second order kinetic model. The values of ΔG, ΔS, and ΔH suggest that the adsorption process is spontaneous and endothermic. Additionally, the adsorption process is easily reversible, enabling the reuse of the adsorbate even after fifth cycle. Further, density functional theory (DFT) simulations demonstrated that the CT and RS adsorption onto the AC adsorbent is favorable. Among the oxygen functional groups analysed, the carboxyl group showed the greatest effect on the adsorption process, exhibiting the most negative adsorption energy at -44.869 (CT) and -45.082 kJmol-1 (RS), respectively. Therefore, the activated carbon derived from CAB has significant potential for effectively removing phenolic contaminants from wastewater.

Highly Active and Stable P2O5 Catalysts Supported on Mesoporous Silica Promoted with Ce for the O‐Methylation of Catechol

AbstractP2O5 has been widely used as an acid‐base catalyst for the O‐methylation of catechol to guaiacol due to its suitable acid strength; however, its stability, which is a significant concern for industrial applications, has not seen significant breakthroughs. Herein, we developed a facile impregnation strategy to synthesize Ce promote P2O5 supported on mesoporous silica (CeP/SBA). The CeP/SBA‐500 carbonized at 500 °C exhibited the highest catalytic activity with a catechol conversion of 71.5 %. The high activity stems from the addition of Ce, forming CePO4, which exhibits improved surface acidity compared to P2O5. Importantly, chemisorption and in situ infrared studies revealed that CePO4 shows stronger adsorption of catechol, which then rapidly converts to guaiacol. The CeP/SBA‐500 exhibits excellent stability with no activity decrease after 10 h of continuous flow reaction, attributed to the absence of a decrease in CePO4 surface acidity.

Interaction of phenolic compounds with functionalized TiO2: Enhanced catechol adsorption and cooperative phenol adsorption

A commercial TiO2 sample functionalized with 3-aminopropyltrimethoxysilane (APTMS) and 4-carboxyphenylboronic acid (CPBA), has been previously proposed as a suitable photocatalyst to perform selective photocatalytic degradation of pollutants in aqueous streams, while avoiding the oxidation of valuable catechol simultaneously present in the reacting medium. In the present study, we highlight the adsorption mechanisms underlying the higher affinity of catechol, compared to phenol, with the surface of modified TiO2, quantitatively justifying the photocatalytic selective degradation results previously obtained. Moreover, a cooperative adsorption mechanism of phenol onto the TiO2 sample modified with APTMS has been for the first time observed. The resulting sigmoidal adsorption isotherms, satisfactorily fitted with the Hill model, could be attributed to the enhanced surface hydrophobicity and, more importantly, to alterations of the folding of APTMS molecules on the TiO2 surface occurring upon increasing the concentration of the phenolic compounds.Photocatalytic tests revealed that the existence of boronate groups on the surface of TiO2 hinders the photocatalytic degradation of catechol and facilitates a swifter oxidation of phenol. These findings confirm the potential for selective photocatalytic degradation, in line with modern conceptions of innovative and environmentally sustainable wastewater treatments.

Adsorption Behaviors and Mechanism of Phenol and Catechol in Wastewater by Magnetic Graphene Oxides: A Comprehensive Study Based on Adsorption Experiments, Mathematical Models, and Molecular Simulations.

This study provides a comprehensive analysis of the adsorption behaviors and mechanisms of phenol and catechol on magnetic graphene oxide (MGO) nanocomposites based on adsorption experiments, mathematical models, and molecular simulations. Through systematic experiments, the influence of various parameters, including contact time, pH conditions, and ionic strength, on the adsorption efficacy was comprehensively evaluated. The optimal contact time for adsorption was identified as 60 min, with the observation that an increase in inorganic salt concentration adversely affected the MGOs' adsorption capacity for both phenol and catechol. Specifically, MGOs exhibited a superior adsorption performance under mildly acidic conditions. The adsorption isotherm was well represented by the Langmuir model, suggesting monolayer coverage and finite adsorption sites for both pollutants. In terms of adsorption kinetics, a pseudo-first-order kinetic model was the most suitable for describing phenol adsorption, while catechol adsorption conformed more closely to a pseudo-second-order model, indicating distinct adsorption processes for these two similar compounds. Furthermore, this research utilized quantum chemical calculations to decipher the interaction mechanisms at the molecular level. Such calculations provided both a visual representation and a quantitative analysis of the interactions, elucidating the underlying physical and chemical forces governing the adsorption phenomena. The findings could not only offer crucial insights for the treatment of coal industrial wastewater containing phenolic compounds with bridging macroscopic observations with microscopic theoretical explanations but also advance the understanding of material-pollutant interactions in aqueous environments.

Polyphenol oxidase inactivation from apple juice by Al-based metal–organic frameworks: New anti-browning strategy in fruits and vegetables

Polyphenol oxidase (PPO) is critical due to enzymatic browning in fruits and vegetables, developing economic impact in fruits industry. Metal-Organic Frameworks (MOF) have shown interesting characteristics such as water stability, low toxicity, and good adsorption yield, making them good candidates for PPO inactivation. Al-based-MOFs, MIL-53(Al), DUT-5, and MIL-110 were tested as PPO inactivators in apple juice by enzyme-MOF interactions at r.t. through two possible mechanisms, i) substrate scavengers (substrates:catechol and 4-methylcatechol) or ii) enzyme activity modifiers. The scavenging behavior of Al-based-MOFs was moderate, in the same magnitude, being catechol adsorption better than 4-methylcatechol. PPO activity was reduced by at least 70% by MIL-53(Al)/DUT-5 in 10/30 min respectively, and MIL-110 inactivated PPO in 50 min with some structural modifications. Enzyme-MOF interactions are major responsible for PPO inactivation. This could be a new applicability of MOFs, as an alternate PPO inactivation process, easily included in juice processing, retaining sensorial/nutritional properties, developed at r.t thus energy-cost-effective.

A Magnetite Composite of Molecularly Imprinted Polymer and Reduced Graphene Oxide for Sensitive and Selective Electrochemical Detection of Catechol in Water and Milk Samples: An Artificial Neural Network (ANN) Application

In the present study, a stable and more selective electrochemical sensor for catechol (CC) detection at magnetic molecularly imprinted polymer modified with green reduced graphene oxide modified glassy carbon electrode (MIP/rGO@Fe3O4/GCE). Two steps have been applied to achieve the imprinting process: (1) adsorption of CC on the surface of the polypyrrole (Ppyr) during the polymerization of pyrrole and (2) the green extraction of the template (CC) from the mass produced. Hence, the present paper doesn’t present the first use of MIP technology for CC identification but, it presents a new extraction process. The MIP/rGO@Fe3O4/GCE was characterized by voltammetry techniques and exhibited a wide linear range from1 50 μM of CC while the detection limits were estimated to be around 4.18 nM CC and limit of quantification in the range of 12.69 nM CC. Furthermore, the prepared MIP-based sensor provided outstanding electroanalytical performances including high selectivity, stability, repeatability, and reproducibility. For the accurate estimation of CC concentrations, an artificial neural network (ANN) was developed based on the findings of the study. The MIP/rGO@Fe3O4/GCE exhibits excellent stability with a very important selectivity and sensitivity. The analytical testing of the modified electrode has been analyzed in water and commercial milk samples and provided adequate recoveries.

Density Functional Evaluation of Catechol Adsorption on Pristine and Reduced TiO2(B)(100) Ultrathin Sheets for Dye-Sensitized Solar Cell Applications

The introduction of defects is one of the most recurrent pathways to generate modifications to materials' electronic structure and surface reactivity. In this work, calculations based on the density functional theory (DFT) were applied to study the electronic properties of pristine and reduced TiO2(B)(100) ultrathin sheets to evaluate their potential as a semiconductor material for dye-sensitized solar cells (DSSCs). It was carried out by introducing vacancy defects on these surfaces and then adsorbing a catechol molecule, used as a model of a direct electron injection sensitizer (type-II dye), in different interaction configurations. Geometric, energetic, and electronic analyses were performed, focusing on the electronic structure changes and charge transfer between the dye and surface during molecular adsorption. The obtained results seem to indicate that a thickness of four layers is adequate to obtain a satisfactory slab model approximation of the TiO2(B)(100) surface. The presence of oxygen vacancy states among the majority of the reduced surfaces was observed as well as a reduction of the band gap energy value. Additionally, the adsorption of catechol in the reduced surface induced an increase in light absorption compared to the pristine model. These attributes suggest that reduced ultrathin sheets of TiO2(B) could be a suitable candidate as a photoelectrode for DSSC applications.

Use of Biochar Prepared from the Açaí Seed as Adsorbent for the Uptake of Catechol from Synthetic Effluents.

This work proposes a facile methodology for producing porous biochar material (ABC) from açaí kernel residue, produced by chemical impregnation with ZnCl2 (1:1) and pyrolysis at 650.0 °C. The characterization was achieved using several techniques, and the biochar material was employed as an adsorbent to remove catechol. The results show that ABC carbon has hydrophilic properties. The specific surface area and total pore volume are 1315 m2·g-1 and 0.7038 cm3·g-1, respectively. FTIR revealed the presence of oxygenated groups, which can influence catechol adsorption. The TGA/DTG indicated that the sample is thermally stable even at 580 °C. Adsorption studies showed that equilibrium was achieved in <50 min and the Avrami kinetic model best fits the experimental data, while Freundlich was observed to be the best-fitted isotherm model. Catechol adsorption on ABC biochar is governed by van der Waals forces and microporous and mesoporous filling mechanisms. The Qmax is 339.5 mg·g-1 (40 °C) with 98.36% removal of simulated effluent, showing that açaí kernel is excellent biomass to prepare good biochar that can be efficiently used to treat real industrial effluents.

Remarkable enhancement in catechol sensing by the decoration of selective transition metals in biphenylene sheet: A systematic first-principles study

Motivated by the recent successful synthesis of biphenylene structure (Fan et al 2021 Science 372 852), we have explored the sensing properties of this material towards the catechol biomolecule by performing the first-principles density functional theory and molecular dynamics simulations. Pristine biphenylene sheet adsorbs catechol molecule with a binding energy of −0.35 eV, which can be systematically improved by decorating the transition metals (Ag, Au, Pd, and Ti) at various possible sites of biphenylene. It is observed that the catechol molecule is adsorbed on Pd and Ti-decorated biphenylene sheets with strong adsorption energies of −1.00 eV and −2.54 eV, respectively. The interaction of the catechol molecule with biphenylene and metal-decorated biphenylene is due to the charge transfer from the O-2p orbitals of the catechol molecule to the C-2p orbitals of biphenylene and d-orbitals of metals in metal-decorated biphenylene, respectively. From the Bader charge calculation, we found that 0.05e amount of charge is transferred from the catechol molecule to pristine biphenylene, which gets almost double (∼0.1e) for the Ti-decorated biphenylene sheet. The diffusion energy barrier for the clustering of the Pd and Ti atoms comes out to be 2.39 eV and 4.29 eV, computed by performing the climbing-image nudged elastic band calculations. We found that the catechol molecule gets desorbed from the pristine biphenylene sheet at 100 K but remains attached to metal (Pd, Ti) decorated biphenylene sheets at room temperature by performing the ab-initio molecular dynamics simulations. The Ti-decorated biphenylene sheet has more sensitivity toward catechol adsorption while the Pd-decorated biphenylene sheet has a suitable recovery time at 500 K. The results suggest that the Pd and Ti-decorated biphenylene sheets are promising materials for catechol detection.

Adsorption of catechol on a weak-base anion exchanger prepared by a novel template-induced method: Batch tests

In this work, a weak-base anion exchanger (TIR) was synthesized through a novel simplified strategy based on the principle of surface imprinting polymer (SIP) to selectively remove the catechol from aqueous solution. The chloromethylated polystyrene beads (CMPS), diethylamine and catechol were employed as the carrier, amination reagent and template respectively in the study. The N2 adsorption-desorption isotherms and Fourier-transform infrared spectroscopy (FT-IR) indicated that the functional group had been successfully grafted onto the CMPS, which directly constructed template-induced adsorption sites in the pore structure. When the solution was neutral, both TIR and CR could reach the maximum adsorption capacity of catechol. Fitting results of adsorption isotherms suggested that catechol adsorption on the TIR surface might occur in a monolayer manner and was endothermic. The maximum adsorption capacity of TIR (1.60 mmol/g) fitted by Langmuir model was almost twice than that of conventional resin (CR), while the kinetic properties of TIR did not decrease significantly. In the salt (NaCl or Na2SO4) concentration range of 20 to 80 g/L, the adsorption capacity of TIR was about 10% to 50% higher than that of CR. For resorcinol and quinol, as two competitors in binary system, the selectivity coefficients (α) of TIR to catechol were 1.49 and 5.83, respectively, which were significantly higher than those of CR (0.72 and 1.58, respectively). Adsorption behaviors in different solvents and FT-IR spectra after adsorption verify that the main interactions between TIR and catechol were electrostatic attraction, hydrogen bonding, hydrophobic interaction and π-π interaction. The regeneration experiment and FT-IR spectrum after desorption showed that the structure of TIR was stable before and after desorption, and the desorption rate could reach more than 90%. This study showed TIR had a superior selective adsorption capacity for catechol and provided a facile strategy to prepare selective adsorbent for the target phenolic pollutant.

Effects of coverage, water, and defects on Catechol/TiO2 interface

Catechol adsorbed on TiO2 is one of the simplest models to explore the relevant properties of dye-sensitized solar cells. However, the effects of water and defects on the electronic levels and the excitonic properties of the catechol/TiO2 interface have been rarely explored. Here, we investigate four catechol/TiO2 interfaces aiming to study the influence of coverage, water, and defects on the electronic levels and the excitonic properties of the catechol/TiO2 interface through the first-principles many-body Green’s function theory. We find that the adsorption of catechol on the rutile (110) surface increases the energies of both the TiO2 valence band maximum and conduction band minimum by approximately 0.7 eV. The increasing coverage and the presence of water can reduce the optical absorption of charge-transfer excitons with maximum oscillator strength. Regarding the reduced hydroxylated TiO2 substrate, the conduction band minimum decreases greatly, resulting in a sub-bandgap of 2.51 eV. The exciton distributions in the four investigated interfaces can spread across several unit cells, especially for the hydroxylated TiO2 substrate. Although the hydroxylated TiO2 substrate leads to a lower open-circuit voltage, it may increase the separation between photogenerated electrons and holes and may therefore be beneficial for improving the photovoltaic efficiency by controlling its concentration. Our results may provide guidance for the design of highly efficient solar cells in future.

Catechol sensor based on pristine and transition metal embedded holey graphyne: a first-principles density functional theory study.

To develop a highly sensitive and selective biosensor for detecting noxious biomolecules from the environment, we examined catechol (Cc) adsorption in pristine and transition metal (TM = Sc, Cu, and Pd) embedded 2D holey graphyne (hGY) monolayers using the first-principles density functional theory method. The interaction between Cc and the pristine hGY is purely weak, and hence the response of the sensing device will be difficult to detect. Therefore, the TM doping strategy is adopted to improve the sensitivity. According to our findings, Sc binds strongly to the hGY monolayer, with a binding energy of -4.09 eV and a charge transfer of 1.89e from the valence orbitals of Sc to the C 2p orbitals. Later on, the Cc adsorption on the TM-embedded hGY was investigated. The interaction of Cc with the transition metal involves charge transfer from Cc to the metal d orbital. A large binding energy of -3.22 eV and a significant charge transfer of about 0.9e from the O 2p orbitals of Cc to the valence orbital of Sc suggest that the Sc embedded hGY monolayer is a good choice for the efficient sensing of Cc molecules. Furthermore, ab initio MD simulations confirmed the structural stability of the Sc + hGY system at room temperature. We strongly believe that this theoretical work will aid the experimentalists in designing and developing 2D semiconducting nanolayer-based biosensors for commercial purposes.

Application of borophene as catechol sensor: a computational study.

The efficacy of borophene (BP) as catechol (CC) sensor was explored using density functional theory (DFT) method. All calculations were performed at B3LYP level of theory and 6-31 + G(d) basis set employing the dispersion correction term of Grimme to consider dispersion interactions. The CC molecule is adsorbed on top of BP horizontally with the adsorption energy (Eads) of about - 13.5kcal·mol-1. The HOMO and LUMO levels of nanosheet destabilize by about 0.36 and 0.14eV, respectively, going from bare BP to BP-CC complex. Therefore, the Eg value decreases by about 10.5% upon adsorption process, which is a reasonable energy gap change for detection of CC. The negligible difference between the work function values (Φ, defined as the minimum amount of the energy needed to remove an electron from a solid to a point in the vacuum immediately outside the solid surface) of BP and its complex with CC indicates that the BP sheet is not an appropriate Φ-type sensor (in these sensors, adsorption of a chemical changes the gate voltage and produces an electrical signal that leads to the detection of chemical agent) for CC detection. The electrical conductivity of BP becomes 72 times higher after CC adsorption. The time needed for CC desorption from BP sheet is 7.6ns, based on conventional transition state theory, showing that BP benefits from a short recovery time. The effect of CC concentration was explored by adsorption of 2 and 3 CC molecules on top of BP nanosheet and the results showed that the sensor response does not change by increasing the CC concentration. Also, the effect of lateral dimensions of BP on the adsorption energy was explored and it was shown that Eads increases by enlargement of the nanosheet.

Surface modification of BaTiO3 with catechol surfactant and effects on cold sintering

The sintering of functionalized particles is an approach often used to obtain high performance functional ceramics. When molecular surfactants are used to functionalize particles, conventional sintering cannot be applied due to extremely high processing temperatures. Here, BaTiO3 particles are grafted with different coverages using a catechol (CA) surfactant, and then these particles are densified under cold sintering with a (BaOH2)⋅8H2O transient flux. The adsorption of CA is equilibrated with various concentrations on BaTiO3 particles at room temperature. The modeling (Langmuir and Freundlich adsorption) and the quantification (UV–vis absorption and thermogravimetric analysis) of CA coverage enable us to rigorously determine the degree of functionalization and conduct thorough cold sintering kinetics investigations as a function of CA coverage using a dilatometer. Microstructure is observed with electron microscopy techniques to determine the grain and grain boundary interfaces that result with the competition of surfactant coverage and densification driven by the dissolution and reprecipitation processes at the interfaces. A mechanism with the retardation of cold sintering kinetics is discussed based on these experimental observations.

Atomic Layer Deposition of Electrocatalytic Insulator Al2O3 on Three-Dimensional Printed Nanocarbons.

The advantages of three-dimensional (3D) printing technologies, such as rapid-prototyping and the freedom to customize electrodes in any design, have elevated the benchmark of conventional electrochemical studies. Furthermore, the 3D printed electrodes conveniently accommodate other active layers for diverse applications such as energy storage, catalysis, and sensors. Nevertheless, to enhance a complex 3D structure while preserving the fine morphology, conformal deposition by atomic layer deposition (ALD) technique is a powerful solution. Herein, we present the concept of coating Al2O3 by ALD with different thicknesses from 20 to 120 cycles on the 3D printed nanocarbon/PLA electrodes for the electrocatalytic oxidation of catechol as an important biomarker. Overall, 80 ALD cycle Al2O3 achieved an optimum thickness for catechol electrocatalysis. This is resonated with the enhanced adsorption of catechol at the electrode surface and efficient electron transfer, according to the two-proton, two-electron-transfer mechanism, as well as for the passivation of surface defects of the nanocarbon electrode. This work compellingly demonstrates the prospect of 3D printed electrodes modified by a functional layer utilizing a low-temperature ALD process that can be extended to other arbitrary surfaces.

Adsorption of catechol by Zr-loaded carbon nanotubes from solution

Adsorption of catechol by Zr-loaded carbon nanotubes from solution

Boronate affinity imprinted Janus nanosheets for macroscopic assemblies: From amphiphilic surfactants to porous sorbents for catechol adsorption

The fabrication of macroscopic assemblies from Janus-like nanosheets to porous sorbents, that can be used for highly efficient pollutant uptake in waters is a very meaningful work. Here, Janus nanosheets (NS-1) with amino groups on one side and Cl initiators on the other side are firstly prepared by interfacial sol-gel process from anisotropic emulsion droplets. Amphiphilic NS-1 can spontaneously assemble at the water/oil interface of high internal phase emulsions (HIPEs) to reduce the interfacial tension, and can also be firmly immobilized onto porous foam substance (NS-1-HIPEs) by initiating the continuous phase. Boronate affinity imprinted Janus nanosheets for macroscopic assemblies (NS-1-MIPs) can be obtained via selectively grafting imprinted polymers onto one side of Janus nanosheets, which can be applied for sorptive extraction of cis-diol-containing catechol. Under the conditions of 308 K, 298 K (pH = 8.5), the saturated adsorption capacity of NS-1-MIPs is 128.1 μmol g−1 and 99.6 μmol g−1, respectively, and the Langmuir model can well describe the equilibrium performance. In addition, NS-1-MIPs possess quick rebinding kinetics in 40 min, and the pseudo-second-order model fits well with the adsorption process, and the adsorption rate is controlled by the chemical adsorption. After 7 cycles of regeneration, adsorption capacity of NS-1-MIPs remains 95.57% of the initial value. This work opens a new pathway to prepare MIPs composite sorbents by the interfacial assembly strategy, and provides for a strategy to overcome the bottleneck of engineering nanoparticles for pollutant uptake.

Facile Electrochemical Demethylation of 2-Methoxyphenol to Surface-Confined Catechol on the MWCNT and Its Efficient Electrocatalytic Hydrazine Oxidation and Sensing Applications.

Owing to its biological significance, preparation of stable surface-confined catechol (CA) is a long-standing interest in electrochemistry and surface chemistry. In this connection, various chemical approaches such as covalent immobilization (using amine- and carboxylate-functionalized CA, diazotization-based coupling, and Michael addition reaction), self-assembled monolayer on gold (thiol-functionalized CA is assembled on the gold surface), CA adsorption on the ad-layer of a defect-free single-crystal Pt surface, π–π bonding, CA pendant metal complexes, and CA-functionalized polymer-modified electrodes have been reported in the literature. In general, these conventional methods are involved with a series of time-consuming synthetic procedures. Indeed, the preparation of a surface-fouling-free surface-confined system is a challenging task. Herein, we introduce a new and facile approach based on electrochemical demethylation of 2-methoxyphenol as a precursor on the graphitic surface (MWCNT) at a bias potential, 0.5 V vs Ag/AgCl in neutral pH solution. Such an electrochemical performance resulted in the development of a stable and well-defined redox peak at Eo’ = 0.15 (A2/C2) V vs Ag/AgCl within 10 min of preparation time in pH 7 phosphate buffer solution. Calculated surface excess (16.65 × 10–9 mol cm–2) is about 10–1000 times higher than the values reported with other preparation methods. The product (catechol) formed on the modified electrode was confirmed by collective electrochemical and physicochemical characterizations such as potential segment analysis, TEM, Raman, IR, UV–vis, GC–MS, and NMR spectroscopic techniques, and thin-layer chromatographic studies. The electrocatalytic efficiency of the surface-confined CA system was demonstrated by studying hydrazine oxidation and sensing reactions in a neutral pH solution. This new system is found to be tolerant to various interfering biochemicals such as uric acid, xanthine, hypoxanthine, glucose, nitrate, hydrogen peroxide, ascorbic acid, Cu2+, and Fe2+. Since the approach is simple, rapid, and reproducible, a variety of surface-confined CA systems can be prepared.

Adsorption of catechol and hydroquinone on titanium oxide and iron (III) oxide

Abstract The adsorption of catechol (CAT) and hydroquinone (HYD) on the surface of TiO2 (anatase) and Fe2O3 (hematite) were investigated using attenuated total reflectance Fourier transform infrared spectroscopy. Linear and nonlinear regression together with error analysis methods were employed to identify the model that best explains the experimental data. Adsorption on these oxides was found to increase as pH was raised, reaching a maximum at the pHpzc of the respective oxide and decreasing as pH increased. Among the kinetic and adsorption models investigated, pseudo-second-order kinetic model and Freundlich adsorption model were found to fit the experimental data well, respectively. The maximum adsorption capacity for CAT was found to be 122.8 ± 33.1 mg g−1 and 361.2 ± 0.1 mg g−1, on TiO2 and Fe2O3, respectively, averaged between pH, kinetic and adsorption studies. For HYD on Fe2O3, the adsorption capacities were 86.12 mg g−1 and 58.49 mg g−1, while adsorption on TiO2 was 63.2 mg g−1 and 351.7 mg g−1, as calculated from pH and kinetic studies, respectively. It was also observed that TiO2 had higher HYD adsorption capacity than Fe2O3, while CAT adsorption capacity was higher in Fe2O3, than in TiO2, confirming that the nature of adsorbent can influence the adsorption of substrates on their surfaces.

Investigating Catechol Surface Modification of TiO2 for the Development of High Performance Photoelectrochemical Biosensors

DNA biosensors are chemical sensors which are used to detect concentrations of specific DNA sequences or register DNA related biological events. There is significant interest in research into the design and optimization of DNA biosensors as they allow for rapid detection of cancers and infectious diseases 1,2. Photoelectrochemical (PEC) techniques can be applied to achieve high performance DNA biosensors with low cost and ultra-sensitivity. In this work, we explored the surface modification of TiO2 nanoparticles (NP) with various catechol molecules and used them to fabricate photoelectrodes for signal-off PEC DNA biosensors. Catechol modification provided dual functionality to the TiO2 NP photoelectrodes: it enhanced their PEC response and provided a molecular linker for attaching probes that capture target DNA.The surface modification of TiO2 NPs was done by adding aqueous solutions of catechol molecules to a suspension of TiO2. Adsorption of catechol on TiO2 took place very rapidly, indicated by a quick change in the colour of the suspension. The catechol-modified TiO2 suspensions were dropdeposited on indium tin oxide coated polyethylene terephthalate (ITO/PET) substrates and oven baked to produce photoelectrodes for the PEC DNA biosensor. Seven catechol molecules were used for surface modification: Caffeic acid (CA), 3,4-Dihydroxybenzaldehyde (DHBA), 3,4-Dihydroxybenzoic acid (DHB), 3,4-Dihydroxy-L-phenylalanine (DOPA), 3,4-Dihydroxyphenylacetic acid (DHPL), 2,3,4-Trihydroxybenzaldehyde (THBA), 2,3,4-Trihydroxybenzoic acid (THB). The photoelectrodes were optically characterized via ultraviolet/visible (UV/vis) spectroscopy and incident photon-to-electron conversion efficiency (IPCE). Additionally, the PEC current of the photoelectrodes were measured using chronoamperometry under white light excitation.Compared against unmodified TiO2, the UV/Vis spectroscopy and IPCE displayed increased light absorption in the visible range and red-shifting for the catechol-modified TiO2 photoelectrodes. This correlated to a great improvement in photocurrent generation. CA-modified TiO2 resulted in the largest increase in photocurrent, over 20 times from the unmodified TiO2 and therefore it was used as the basis for our PEC DNA biosensor. Single stranded DNA (ssDNA) probes were deposited onto the photoelectrodes, followed by target ssDNA deposition. The difference in PEC current after probe deposition and target deposition indicated the concentration of target DNA. A calibration curve was plotted with PEC current density as a function of target DNA concentration, which decreased logarithmically and ranged from 100 nM – 100 fM. A limit of detection (LOD) of 2.38 pM was estimated at a signalto-noise ratio of 3Sx/y (where Sx/y is the root-mean-square error (RMSE)).It is evident from our investigation that functionalizing TiO2 with catechol ligands greatly improves its optical properties which lead to a greater PEC current generation. In particular, high PEC current resulting from the combination of CA and TiO2 can form the basis for high-performance signal-off PEC DNA biosensors with a high dynamic range and low LOD. 1. Beltrán, A. P. & García, M., DNA biosensors and biomarkers to cancer detection. International Journal of Biosensors and Bioelectronics, 4(1), 20-21 (2018)2. Chua, A., Yean, C. Y., Ravichandran, M., Lim, B. & Lalitha, P., A Rapid DNA Biosensor for the Molecular Diagnosis of Infectious Disease. Biosensors and Bioelectronics, 26(9), 3825-3831 (2011)