Adsorption Of Benzotriazole Research Articles

Probing Ti–doped (Al–Ga) surface as Nanosensor for adsorbing the S- & N-containing heterocyclic compounds

Aluminum–Gallium doped with titanium by using ONIOM method through structural, electrical, and thermodynamic properties was studied in detail. Crystal structure of Ti–(Al–Ga) surface was coated by S- & N-heterocyclic carbenes of benzotriazole (BTA), 2-mercaptobenzothiazole (2MBT), 8-hydroxyquinoline (8HQ) and 3-amino-1,2,4-triazole-5-thiol (ATR). The “NMR” spectroscopy of the adsorption of BTA, 2MBT, 8HQ, and ATR on the Ti–doped Al–Ga nanoalloy surface represents that this surface can be employed as the magnetic S- & N-heterocyclic carbene sensors. In fact, “Ti” site in “Ti–(Al–Ga)” nanoalloy surface has bigger interaction energy amount from “Van der Waals’ forces” with BTA, 2MBT, 8HQ, and ATR that might cause them large stable towards coating data on the nanosurface. It has been estimated that the criterion for choosing the surface linkage of “S” and “N” atom in BTA, 2MBT, 8HQ, and ATR in adsorption sites can be impacted by the existence of close atoms of aluminum and gallium in the “Ti–(Al–Ga)” surface. The fluctuation of “NQR” has estimated the inhibiting role of BTA, 2MBT, 8HQ, and ATR for Ti–doped Al–Ga alloy nanosheet due to “S” and “N” atoms in the benzene cycle of heterocyclic carbenes being near the monolayer surface of ternary “Ti–(Al–Ga)” nanoalloy. Moreover, “IR” spectroscopy has exhibited that Ti–doped Al–Ga alloy nanosheet with the fluctuation in the frequency of intra–atomic interaction leads us to the most considerable influence in the vicinage elements generated due to inter–atomic interaction. Comparison to amounts versus dipole moment has illustrated a proper accord among measured parameters based on the rightness of the chosen isotherm for the adsorption steps of the formation of BTA @Ti–(Al–Ga), 2MBT @Ti–(Al–Ga), 8HQ @Ti–(Al–Ga), and ATR @Ti–(Al–Ga) complexes. Thus, the interval between sulfur, nitrogen and oxygen atoms in BTA, 2MBT, 8HQ, and ATR during interaction with transition metal of “Ti” in “Ti–(Al–Ga)” nanoalloy, (N→Ti, O→Ti, S→Ti), has been estimated with relation coefficient of R² = 0.9509. Thus, the present has exhibit the influence of “Ti” doped on the “Al–Ga” surface for adsorption of S- & N-heterocyclic carbenes of BTA, 2MBT, 8HQ, and ATR by using theoretical methods. Furthermore, the “partial electron density” or “PDOS” has estimated a certain charge assembly between Ti–(Al–Ga) and S– & N–heterocycles of BTA, 2MBT, 8HQ, and ATR which can remark that the complex dominant of metallic features and an exact degree of covalent traits can describe the augmenting of the sensitivity of “Ti–(Al–Ga)” surface as a potent sensor for adsorption of BTA, 2MBT, 8HQ, and ATR heterocycles.

Rapid adsorption of benzotriazole onto oxidized carbon cloth as an easily separable adsorbent

A commercial carbon cloth (CC) was oxidized by HNO3 acid and the features of the plain and oxidized CC were evaluated. The results of characterization illustrated that HNO3 oxidization duplicated the oxygen-containing functional groups and the surface area of the CC. The adsorption performance of the plain and oxidized CC (Oxi-CC) toward benzotriazole (BTR) was compared. The results disclosed that the uptake of BTR by oxidized CC was greater than the plain CC. Thence, the affinity of oxidized CC toward BTR was assessed at different conditions. It was found that the adsorption was quick, occurred at pH 9 and improved by adding NaCl or CaCl2 to the BTR solution. The kinetic and isotherm studies revealed that the surface of Oxi-CC is heterogeneous and the adsorption of BTR follows a physical process and forms multilayer over the Oxi-CC surface. The regenerability and reusability study illustrated that only deionized water can completely regenerate the Oxi-CC and that the Oxi-CC can be reused for five cycles without any loss of performance. The high maximum adsorption capacity of Dubinin–Radushkevich isotherm model (252 mg/g), ease of separation and regeneration, and maintaining the adsorption capacity for several cycles revealed the high efficiency and economical and environmental feasibility of Oxi-CC as an adsorbent for BTR.

Design of anti-mildew smart microcapsules with chitosan as encapsulant for advanced electronic packaging epoxy coating

Moisture protection, anti-mildew and anti-corrosion are essential to guarantee the normal service of electronic devices. Although the epoxy holds great potential for electronic packaging, its inferior anti-corrosive performance and anti-mildew capability significantly affect the lifespan of the coating and thus impede further technological advances in electronic devices. To address this concern, herein, we fabricate environmental-friendly anti-mildew smart microcapsules (MCs) by encapsulating benzotriazole (BTA) loaded halloysite clay nanotubes (HNTs) with chitosan (CTS). The coating presents superior anti-mildew property with 5 wt% MCs addition. Furthermore, the charge transfer resistance (Rct) of T2 copper beneath the coating is three orders of magnitude larger after 35 days' immersion, which confirms a significantly promoted anti-corrosive performance for the coating. Moreover, mechanism study shows that such enhanced corrosion protective performance of proposed coating benefits from an excellent self-healing property enabled by a sustainable release of BTA with water and dual-pH sensitivity as well as effective adsorption of BTA on metal surface. It is further uncovered that the release rate of BTA is simultaneously determined by solubility of BTA, acid pH sensitivity of CTS and interaction between BTA and CTS. In addition, mechanical properties of coatings are enhanced with the tensile strength and elongation significantly increased, while the wet adhesion force (72 h) is also enlarged from 4.03 MPa to 7.22 MPa. Such a delicate design of environmental-friendly anti-mildew smart MCs not only enhances the corrosion protective property and the anti-mildew performance of the electronic packaging coatings, but also can facilitate the fabrication of other multifunctional organic coatings by utilizing multifunctional inhibitor or polyelectrolytes.

Fabrication of chemisorbed film on ultrafine-grained steels for corrosion inhibition in saline solution

The corrosion inhibition performance and film-forming mechanism of benzotriazole on ultrafine-grained steels in 3.5 wt.% NaCl solution was studied by electrochemical impedance spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and surface morphology analysis. The results show that grain ultra-refinement leads to excellent inhibition performance and different film-forming mechanisms of benzotriazole on low alloy steels. This attributes to the large increase in the grain boundary densities that accelerated the adsorption of benzotriazole and induced chemisorption of benzotriazole on the surface of low alloy steels. The results allow for a comprehensive understanding of the corrosion inhibition and film-forming mechanism of benzotriazole on mild steel in near-neutral saline solutions.

Copper adatoms mediated adsorption of benzotriazole on a gold substrate

The adsorption of organic molecules on metal surfaces is often mediated by metal adatoms, however their effect on the geometry of the resulting supramolecular structure can be difficult to determine. Herein, the role played by reactive copper atoms in the adsorption chemistry of benzotriazole (BTAH), an organic corrosion inhibitor for copper well-known for forming adatom mediated supramolecular structures, on an inert substrate, Au(111), has been investigated in an ultra-high vacuum environment using a combination of complementary surface sensitive techniques and density functional theory calculations. Pseudo-ordered and hydrogen bonded flat-lying assemblies convert into ordered -[CuBTA]n- flat-lying organometallic species of well-defined stoichiometry upon addition of copper atoms from the gas phase onto an Au(111) surface, which has been pre-dosed with BTAH. The formation and characterisation of these organometallic species are discussed in the light of the experimental results and computational modelling. The combination of complementary experimental and computational methods is crucial in order to obtain a thorough characterisation of such a complex system. The final supramolecular structure shows previously unseen BTA phases, which are favoured by the adsorption distribution of copper adatoms on Au(111), and are stable up to 500 K.

Preparation, characterization, and application of modified magnetic biochar for the removal of benzotriazole: process optimization, isotherm and kinetic studies, and adsorbent regeneration.

The adsorption of benzotriazole (BTA) by chemically modified magnetic biochar (MMBC) as a cheap and abundant biosorbent was investigated and optimized using response surface methodology (RSM). Initially, the MMBC composite was synthesized and characterized by scanning electron microscopy (SEM) energy dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and Brunauer-Emmett-Teller (BET) techniques. The characterization results confirmed the existence of Fe3O4 in the composite structure, which had uniformly dispersed over biochar (BC) with porous texture. Moreover, the presence of Zn and Cl elements in EDX analysis indicated that the magnetic biochar (MBC) had been modified successfully. The effects of chemical modification methods on the adsorption capacity of magnetic biochar were investigated. Maximum BTA removal efficiency was demonstrated by MMBC, modifying using ZnCl2 (>99%). Optimization was carried out based on reaction time, BTA concentration and the concentration of adsorbent. Optimum experimental conditions for the removal of BTA from aqueous solutions were found to be 35 min of reaction time, 0.55 g/L of adsorbent, and 50 mg/L of initial BTA concentration. At these optimal conditions, the predicted BTA adsorption efficiency was 92.6%. The adsorption process followed the Avrami fractional-order reaction kinetic and the Langmuir adsorption isotherm with the maximum adsorption capacity of 563.1 mg/g. The values of thermodynamic parameters demonstrated that the adsorption of BTA on ZnCl2-MBC is endothermic and spontaneous. Under optimum usage of MMBC, the adsorptive removal efficiency of BTA non-significantly decreased from 99.2 to 93.9% after the 5th cycle. Thus, MMBC can be recommended as an environmentally friendly and cost-effective adsorbent to remove micropollutants from water.

Predicting the effect of dissolved humic acid on sorption of benzotriazole to biochar

Dissolved organic matter plays a critical role in affecting sorption properties of biochar for organic contaminants. In this study, dissolved humic acid (DHA) as a representative of dissolved organic matter and oak sawdust-derived biochar as a sorbent were prepared and characterized. Roles of DHA in sorption of benzotriazole (BTA), an emerging organic contaminant, to biochar in different electrolyte solutions were investigated. The results revealed the dual roles of DHA in BTA sorption to biochar. On the one hand, DHA can compete for sites and/or block pores available for BTA to inhibit the adsorption of BTA to biochar. On the other hand, the sorbed DHA on biochar can serve as additional partitioning phase to promote the partition of BTA. The finding was in accordance with the site energy distribution analysis of BTA sorption that the site energy of the highest occurring frequency in the DHA-BTA system was lower than that in the DHA-free system (3.41–10.4 versus 13.1–20.1 kJ mol−1). The variation in apparent BTA sorption to biochar affected by DHA was thus a combination of changes in both its partition and adsorption properties. A modified Dual-mode model including the aqueous concentration of DHA was proposed to predict the effect of DHA on BTA sorption to biochar in different electrolyte solutions, which showed good prediction performance with most BTA sorption coefficient (Kd, L g−1) deviations within 0.1 log unit.

Insights into Effects of Metal Cations on the Adsorption of Benzotriazole on Halloysite Nanotubes: An Experimental and DFT Study

Insights into Effects of Metal Cations on the Adsorption of Benzotriazole on Halloysite Nanotubes: An Experimental and DFT Study

Copper Adatoms Mediated Adsorption of Benzotriazole on a Gold Substrate

Copper Adatoms Mediated Adsorption of Benzotriazole on a Gold Substrate

A smart healable anticorrosion coating with enhanced loading of benzotriazole enabled by ultra-highly exfoliated graphene and mussel-inspired chemistry

Graphene-based nanomaterials encapsulated with corrosion inhibitors are promising materials for achieving smart coatings with healable properties. However, the low loading contents of inhibitors (10%–20%) and the cumbersome synthesis processes remain as urgent problems for practical applications. Here, we propose a novel strategy for preparing healable coatings with the enhanced loading of inhibitors enabled by ultra-highly exfoliated graphene and mussel-inspired chemistry. Ultra-highly exfoliated graphene (1355 m2/g) was achieved via a unique one-pot method of H2O2/KOH catalytic exfoliation and etching with residual KOH. Polydopamine (PDA), as a green corrosion inhibitor, effectively promoted the adsorption of benzotriazole (BTA) on graphene via facile co-adsorption. The corrosion perception of this smart coating with the dual healable effect of BTA/PDA was triggered by PDA decomposition from corrosion-induced pH variations. Thus, the coating exhibited an increased impedance modulus (3.31 × 1010 Ω cm2) even after 30 days of immersion (three orders of magnitude higher than that of an epoxy coating), owing to the outstanding barrier effect of the ultra-highly exfoliated graphene and high loading content of inhibitors (30%). This study has a great significance for the design of high-loading smart nanomaterials for sustainable smart systems.

Theoretical and electrochemical analysis on inhibition effects of benzotriazole derivatives (un- and methyl) on copper surface

The corrosion inhibition effects of benzotriazole (BTA) and its derivative-methylbenzotriazole (M-BTA) at molecular level were studied using quantum chemical method. The adsorption mechanism of inhibitors on copper surface was evaluated by Density Functional Theory (DFT) at BLYP/3.5DNP level and Monte Carlo simulation. The inhibition effects of BTA and M-BTA were investigated by chemical reactivity parameters. Both inhibitors have a considerable excess of negative charges around the nitrogen atoms N7 and N8, indicating that they are the coordination sites of the inhibitors. Under the circumstance of gaseous and aqueous phases molecules, the BTA adsorption and M-BTA adsorption on Cu (111) surface was further simulated by Monte Carlo simulations. In addition, the interaction energy between inhibitors and copper was calculated. The electrochemical measurement results confirm that the inhibition effect of 15mM M-BTA is greater than that of BTA, and the inhibition efficiency is up to 96.05%, which is helpful for further study of corrosion system.

Effect of covalent organic framework modified graphene oxide on anticorrosion and self-healing properties of epoxy resin coatings

Graphene oxide (GO) can enhance the corrosion resistance of epoxy coating, but there are problems such as poor filler dispersion and mechanical damage that will reduce the coating corrosion resistance. To resolve these problems, here, we used a facile and green liquid-phase synthetic strategy to grow covalent organic framework (COF) on GO sheets with 1,3,5-Triformylphloroglucinol and p-phenylenediamine as monomers for the COF synthesis. The COF could not only improve the compatibility of GO with epoxy coating, but also act as a nanocontainer for loading corrosion inhibitors. Electrochemical impedance spectroscopy showed that the low-frequency impedance of GO/COF-2% coating immersed in 3.5 wt% NaCl solution for 60 days was 8.58 × 108 Ω cm2. This was one order of magnitude higher than that of GO-2%, showing excellent corrosion resistance. Then, corrosion inhibitor of benzotriazole (BTA) was loaded into GO/COF, where the adsorption and release of BTA was controlled by environmental pH values. Results proved that the GO/COF@BTA-2% reinforced epoxy coating had superior corrosion resistance as well as self-healing ability because of the good compatibility, greater crosslinking density and controllable release of BTA.

Environment-friendly and chromium-free passivation of copper and its alloys

Benzotriazole (BTA) and tolyltriazole (TTA) were used to passivate pure copper and chromium bronze alloys for environmental protection. Using the chemical immersion treatment, a dense film of chromium-free passivation layer was formed on surfaces of both the pure copper and chromium bronze alloys. Microstructure, crystalline phases and chemical bonds of the passivation layers were systematically characterized, and the passivation mechanisms were studied. The passivation layer was mainly consisted of CuO, Cu2O, polymers of Cu-BTA-TTA and Cu(I)BTA-TTA. The formation mechanism of the chromium-free passivation layer was identified as combined oxidation and adsorption, and the main passivation processes included oxidation and dissolution of the matrix, adsorption of BTA and its derivatives, self-stabilization process of the adsorbed film, and filling of passivation film’s voids by oxide particles.

Layered double hydroxides loaded sludge biochar composite for adsorptive removal of benzotriazole and Pb(II) from aqueous solution

In this work, a novel sludge biochar/Zn–Al layered double hydroxide composite (SL) was synthesized in a facile co-precipitation method, and it was used to simultaneously remove benzotriazole (BTA) and lead ion (Pb(II)). Batch adsorption experiments demonstrated that composites with sludge content of 1.0 g (SL-1.0) had a great adsorption performance for BTA and Pb(II). The maximum adsorption capacities of SL-1.0 for BTA and Pb(II) were 239.6 and 226.1 mg g−1, respectively. There was preferential adsorption of BTA in BTA and Pb(II) binary system. The adsorption mechanism analysis indicated that the BTA and Pb(II) adsorption involved electrostatic attraction and chemical bonding with surface functional groups on SL-1.0. Specifically, hydrogen bonding and π-π interaction were mainly ascribed to BTA adsorption, while complexation with surface function groups dominated Pb(II) adsorption. With the advantages of facile synthesis and excellent adsorption capacity, SL-1.0 possesses great potential for simultaneously removing of BTA and Pb(II) from wastewaters.

Effects of benzotriazole and imidazoline on the tribocorrosion behaviors of a WC-based material in saline silica slurries

To improve the performance of impregnated diamond bit in saline drilling fluid, the effects of benzotriazole and imidazoline on the abrasion–corrosion behaviors of a hot-pressed WC-based material and its binder material in saline silica slurries were investigated with a modified abrasion test rig. The morphology of worn surface and corrosion products after tribocorrosion test were analyzed by scanning electron microscopy and Raman spectroscopy, respectively. The results indicated that benzotriazole was a better corrosion inhibitor for the two hot-pressed materials than imidazoline. In abrasion-corrosion tests, the addition of benzotriazole into saline slurry reduced the total weight loss considerably and produced a negative abrasion–corrosion synergy, while imidazoline had hardly noticeable effects, especially to the binder material. The negative synergy could be related to the change in contact condition between abrasive particles and worn surface, owing to the decrease in the adsorption of benzotriazole on the worn surface as a result of cathodic protection. By lowering the corrosion rate of the binder around WC particles and thus lessening the undermining of WC particles, benzotriazole significantly improved the anti-tribocorrosion performance of the WC-based material.

Effect of Dissolved Oxygen on Removal of Benzotriazole from Co during a Post-Co CMP Cleaning

A systematic study of the adsorption of benzotriazole on Co surface and its removal in aqueous solutions was carried out for post-CMP cleaning application. Static etch rate (SER) measurements and electrochemical impedance spectroscopy (EIS) were employed. The experimental results show that BTA adsorbed well on Co surface when it exposed to BTA solution at neutral and alkaline pH. BTA did not adsorb due to active Co dissolution at acidic pH. The effect of dissolved oxygen (DO) concentration in de-ionized (DI) water on the removal of Co-BTA complex layer was investigated. At DI water rinse process after BTA treatment, Co-BTA layer was maintained on Co surface when DO concentration of DI water was low. Interestingly, BTA was removed by DI water with high DO concentration.

Detection of corrosion inhibitor adsorption via a surface-enhanced Raman spectroscopy (SERS) silver nanorods tape sensor

In this work, surface-enhanced Raman scattering (SERS) strategy was utilized for the on-site detection of corrosion inhibitors using a silver nanorods anchored transparent tape sensor. SERS detection realized the intense enhancement of Raman signals from inhibitors to characterize their adsorption behavior on metallic surfaces. Benzotriazole (BTA) molecules were employed as corrosion inhibitors for the protection of AA2024-T3 aluminium alloy in 3.5 wt.% NaCl solution. Electrochemical impedance spectroscopy (EIS) measurement and surface characterization confirmed the superior corrosion inhibition performance of BTA. SERS assessment elucidated that the Raman signals of BTA on AA2024-T3 surface increased gradually with the increase of inhibitor concentration and immersion time. By comparing the EIS and SERS results, it is shown that the SERS intensity was positively correlated with the resistance of the inhibitor film (Rf) and inversely correlated with the capacitance of the inhibitor film (Qf), which indicated that the increased BTA adsorption offered superior inhibitive property against the corrosion of AA2024-T3 in saline solution. The SERS tape developed in this study can be used as a versatile sensor to monitor the dynamic adsorption process of corrosion inhibitors with no restriction on substrate materials.

Corrosion of Copper in 0.1 M Hydrochloric Acid Solution with Benzotriazole as Corrosion Inhibitor

Corrosion inhibition properties of benzotriazole were studied in 0.1 M hydrochloric acid solution for copper samples with different roughness levels using open-circuit potential, potentiodynamic polarization, electrochemical impedance, and weight loss measurements. According to the results, inhibition properties were improved because of an increase in surface roughness leading to an increase in inhibition efficiency (up to 99 and 91% for the rough and smooth surfaces, respectively). Adsorption of benzotriazole on copper surfaces follows Langmuir isotherm. Due to roughening, the adsorption free energy changed from ‒25.9 kJ mol–1 for the polished samples to –27.6 kJ mol–1 for the rough sample. Adsorption of the inhibitor on both surfaces was mainly physisorption. Adsorption entropy values for polished and shot-peened samples were 11.4 and 13 J mol–1 K–1, respectively. All data obtained from weight loss, Tafel polarization, and EIS tests were in good agreement. FTIR test, showed a peak between 740 and 745 cm–1 that is associated with C–H bonds. The intensity of peak was higher in the case of shot-peened samples.

Enhanced corrosion resistance of rebar in carbonated concrete pore solutions by Na2HPO4 and benzotriazole

The corrosion inhibition of a combination of Na2HPO4 (DSP) and benzotriazole (BTA) for rebar in carbonated concrete pore solutions was investigated. Electrochemical methods were adopted to assess the corrosion behaviour of rebar thermodynamically and kinetically. Also, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to detect the composition of oxide films formed on the rebar surface and the surface morphology of rebar, respectively. Results show that there exists an optimum proportion of DSP and BTA to execute the highest corrosion inhibition efficiency. The mixture of DSP and BTA acts as a mixed-type inhibitor, in which DSP behaves as the cathodic inhibitor and BTA acts as the anodic inhibitor. The adsorption of BTA obeys Langmuir adsorption isotherm. High content of BTA could compete with DSP, which leads to low inhibition efficiency.

The relationship between the inhibition performances of three benzo derivatives and their structures on the corrosion of copper in 3.5 wt.% NaCl solution

The relationship between the inhibition performances of three benzo derivatives (Benzimidazole (BIMH), Benzotriazole (BTA) and Benzothiadiazole (BTH)) and their structures on the corrosion of copper in 3.5 wt.% NaCl solution at 30 °C has been studied by electrochemical measurements, surface analysis, quantum chemical calculations and molecular dynamics simulations. The results show that the introduction of sulfur atom into imidazole ring weakens the inhibition effect due to the low hydrophobicity, the large electronegativity and the strong electron binding ability of sulfur atom. However, the introduction of nitrogen atom into imidazole ring enhances the inhibition effect due to the larger adsorption energy. The adsorption of BTH and BIMH belongs to physisorption, and the adsorption of BTA belongs to physicochemical mixed adsorption. The three studied inhibitors tend to be adsorbed on the copper surface in parallel, achieving optimal inhibition effect. This study can help us find new inhibitors with better inhibition performances and improve their inhibition effects.