RESUMO
Electrocatalytic hydrodechlorination (EHDC) is a promising approach to safely remove halogenated emerging contaminants (HECs) pollutants. However, sluggish production dynamics of adsorbed atomic H (H*ads) limit the applicability of this green process. In this study, bimetallic Pd-Cu@MXene catalysts were synthesized to achieve highly efficient removal of HECs. The alloy electrode (Pd-Cu@MX/CC) exhibited better EHDC performance in comparison to Pd@MX/CC electrode, resulting in diclofenac degradation efficiency of 93.3 ± 0.1%. The characterization analysis revealed that the Pd0/PdII ratio decreased by forming bimetallic Pd-Cu alloy. Density functional theory calculations further demonstrated the electronic configuration modulation of the Pd-Cu@MXene catalysts, optimizing binging energies for H* and thereby facilitating H*ads production and tuning the reduction capability of H*ads. Noteably, the amounts and reduction potential of H*ads for Pd-Cu@MXene catalysts were 1.5 times higher and 0.37 eV lower than those observed for the mono Pd electrode. Hence, the introduction of Cu into the Pd catalyst optimized the dynamics of H*ads production, thereby conferring significant advantages to EHDC reactions. This augmentation was underscored by the successful application of the alloy catalysts supported by MXene in EHDC experiments involving other HECs, which represented a new paradigm for EHDC for efficient recalcitrant pollutant removal by H*ads.
Assuntos
Cobre , Paládio , Catálise , Cobre/química , Paládio/química , Poluentes Químicos da Água/química , Adsorção , Halogenação , Técnicas Eletroquímicas/métodos , Eletrodos , Diclofenaco/químicaRESUMO
Triclosan (TCS), a hydrophobic antibacterial agent, is extensive application in daily life. Despite a low biodegradability rate, its hydrophobicity results in its accumulation in waste-activated sludge (WAS) during domestic and industrial wastewater treatment. While anaerobic digestion is the foremost strategy for WAS treatment, limited research has explored the interphase migration behavior and impacts of TCS on WAS degradation during anaerobic digestion. This study revealed TCS migration between solid- and liquid-phase in WAS digestion. The solid-liquid distribution coefficients of TCS were negative for proteins and polysaccharides and positive for ammonium. High TCS levels promoted volatile-fatty-acid accumulation and reduced methane production. Enzyme activity tests and functional prediction indicated that TCS increased enzyme activity associated with acid production, in contrast to the inhibition of key methanogenic enzymes. The findings of the TCS migration behavior and its impacts on WAS anaerobic digestion provide an in-depth understanding of the evolution of enhanced TCS-removing technology.
Assuntos
Metano , Esgotos , Triclosan , Triclosan/farmacologia , Triclosan/metabolismo , Anaerobiose , Metano/metabolismo , Biodegradação Ambiental , Ácidos Graxos Voláteis/metabolismo , Reatores Biológicos , Poluentes Químicos da Água/metabolismo , Eliminação de Resíduos Líquidos/métodosRESUMO
In this study, a Pd@MXene catalyst was synthesized to enhance the electrocatalytic hydrodehalogenation (ECH) of emerging halogenated organic pollutants (HOPs) by improving the dispersibility, catalytic activity, and stability of palladium (Pd). The average size of Pd nanoparticles (NPs) was reduced to 3.62 ± 0.34 nm with a more intensive peak of Pd (111), which facilitated atomic hydrogen (H*) production. The Pd@MX/CC electrode demonstrated superior ECH activity for diclofenac (DCF) degradation, with a reaction rate constant (kobs) 2.48 times higher than that of Pd/CC (without MXene). The satisfactory ECH performance of Pd@MX/CC remained consistent within a wide range of initial DCF concentrations (5-100 mg/L), and no significant ECH attenuation was observed even after up to 10 batches. Furthermore, the high activity of Pd@MX/CC was also observed in the ECH of other halogenated organic pollutants (levofloxacin, tetrabromobisphenol A, and diatrizoate). Density functional theory (DFT) calculations revealed that electronic configuration modulation of the Pd@MXene catalyst optimized binging energies to H* , DCF, and dechlorinated products, thereby enhancing the ECH efficiency of DCF.
RESUMO
The performance of electrochemical reduction is often enhanced by electrode modification techniques. However, there is a risk of microbial colonization on the electrode surface to form biofilms in the treatment of actual wastewater with modified electrodes. In this work, the effects of biofilm formation on modified electrodes with reduced graphene oxide (rGO), platinum/carbon (Pt/C), and carbon nanotube (CNT) were investigated in triclosan (TCS) degradation. With biofilm formation, the TCS degradation efficiencies of carbon cloth (CC), rGO@CC, Pt/C@CC, and CNT@CC decayed to 54.53 %, 59.77 %, 69.19 %, and 53.97 %, respectively, compared to the raw electrodes. Confocal laser scanning microscopy and microbial community analysis revealed that the difference in biofilm thickness and activity were the major influencing factors on the discrepant TCS degradation rather than the microbial community structure. The electrochemical performance tests showed that the biofilm formation increased the ohmic resistance by an order of magnitude in rGO@CC, Pt/C@CC, and CNT@CC, and the charge transfer resistance was increased by 2.45, 3.78, and 7.75 times, respectively. The dechlorination and hydrolysis governed the TCS degradation pathway in all electrolysis systems, and the toxicity of electrochemical reductive products was significantly decreased according to the Toxicity Estimation Software Tool analysis. This study presented a systematic assessment of the biofilm formation on modified electrodes in TCS reduction, and the undisputed experimental outcomes were obtained to enrich the knowledge of implementing modified electrodes for practical applications.
Assuntos
Nanotubos de Carbono , Triclosan , Eletrólise , Eletrodos , Biofilmes , Nanotubos de Carbono/química , PlatinaRESUMO
In this work, the bioelectrochemical system (BES) is a feasible alternative for successfully degrading typical refractory emerging contaminant triclosan (TCS). A single-chamber BES reactor with an initial TCS concentration of 1 mg/L, an applied voltage of 0.8 V, and a solution buffered with 50 mM PBS degraded 81.4 ± 0.2% of TCS, exhibiting TCS degradation efficiency improvement to 90.6 ± 0.2% with a biocathode formed from a reversed bioanode. Both bioanode and biocathode were able to degrade TCS with comparable efficiencies of 80.8 ± 4.9% and 87.3 ± 0.4%, respectively. Dechlorination and hydrolysis were proposed as the TCS degradation pathway in the cathode chamber, and another hydroxylation pathway was exclusive in the anode chamber. Microbial community structure analysis indicated Propionibacteriaceae was the predominant member in all electrode biofilms, and the exoelectrogen Geobacter was enriched in anode biofilms. This study comprehensively revealed the feasibility of operating BES technology for TCS degradation.