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1.
ACS Appl Mater Interfaces ; 16(33): 43498-43511, 2024 Aug 21.
Artículo en Inglés | MEDLINE | ID: mdl-39115165

RESUMEN

Cooperative CO2 photoreduction with tailored organic synthesis offers a potent avenue for harnessing concurrently generated electrons and holes, facilitating the creation of both solar fuels and specialized chemical compounds. However, controlling the crystallization and morphologies of metal-free molecular nanostructures with exceptional photocatalytic activities toward CO2 reduction remains a significant challenge. These hurdles encompass insufficient CO2 activation potential, sluggish multielectron processes, delayed charge-separation kinetics, inadequate storage of long-lived photoexcitons, unfavorable thermodynamic conditions, and the precise control of product selectivity. Here, melem oligomer 2D nanosheets (MNSs) synthesized through pyrolysis are transformed into 1D nanorods (MNRs) at room temperature with the simultaneous engineering of vacancies and morphology. Transient absorption spectral analysis reveals that vacancies in MNRs trap charges, extending charge carrier lifetimes. Additionally, carbon vacancies enhance CO2 adsorption by increasing amine functional centers. The photocatalytic performance of MNRs for CO2 reduction coupled with benzyl alcohol oxidation is approximately ten times higher (CH3OH and aromatic aldehyde production rate 27 ± 0.5 and 93 ± 0.5 mmol g-1 h-1, respectively) than for the MNSs (CH3OH and aromatic aldehyde production rate 2.9 ± 0.5 and 9 ± 0.5 mmol g-1 h-1, respectively). The CO2 reduction pathway involved the carbon-coordinated formyl pathway through the formation of *COOH and *CHO intermediates, as mapped by in situ Fourier-transform infrared spectroscopy. The superior performance of MNRs is attributed to favorable energy-level alignment, enriched amine surfaces, and unique morphology, enhancing solar-to-chemical conversion.

2.
ACS Appl Mater Interfaces ; 16(35): 46200-46215, 2024 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-39164891

RESUMEN

Rational design and precise synthesis of biogenic noble-metal-based catalysts possessing distinctive structure and composition play a crucial role in the chemical industry, enabling sustainable construction of an inclusive range of chemical resources. In this study, we have effectively fabricated Pd@A-CQDs through a straightforward one-pot aqueous protocol assisted by visible light employing renewable biomass-derived amine-rich carbon quantum dots (A-CQDs). The remarkable visible light harnessing capability (bandgap, ca. 2.81 eV), high density (35.7 × 1018 cm-3), and long lifetime (25 ps) of photocharge carriers and amine-rich surface in A-CQDs make them ideal candidates as both reducing and stabilizing agents, thereby facilitating the in situ construction of metallic Pd(0) nanoparticles. Comprehensive physicochemical characterizations have provided compelling evidence for the spherical morphology of Pd@A-CQDs core-shell nanostructures, with ultrathin A-CQDs shells of ca. 1.9 nm and an average diameter of 14 ± 1 nm. The effectiveness of the synthesized Pd@A-CQDs catalysts was assessed in the ligand- and base-free homocoupling reaction of arylboronic acids in water at ambient temperature. The catalytic tests demonstrated the selective production of the homocoupled compound over protodeboronation products with excellent yield and high catalyst recyclability under ambient conditions. The protocol employed exhibited a high TOF (1.05 × 10-2 mol g-1 min-1) and a low E-factor, with a remarkably low palladium loading. XPS analysis confirmed the retention of the metallic nature of the palladium core within the catalysts during the reaction. The catalytic function of the palladium core in conjunction with the A-CQDs shell, along with the promotional effects provided by water and oxygen for the formation of nucleophilic tetravalent boron, was conclusively recognized by 11B NMR and O2-TPD measurements. The obtained experimental results deliver valuable insights into the probable reaction pathway for the homocoupling reaction catalyzed by the Pd@A-CQDs catalysts. Through a comprehensive and sustainable evaluation, the current methodology exhibits superior performance compared to previously documented techniques in relation to estimated circularity and adherence to good manufacturing practices (GMP).

3.
J Colloid Interface Sci ; 660: 756-770, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38271811

RESUMEN

Despite the growing emphasis on eco-friendly nanomaterials as energy harvesters, scientists are actively searching for metal-free photocatalysts to be used in environmental remediation strategies. Developing renewable resource-based carbon quantum dots (CQDs) as the sole photocatalyst to harvest visible light for efficient pollutant degradation is crucial yet challenging, particularly for addressing the escalating issue of water deterioration. Moreover, the photocatalytic decomposition of H2O2 under visible light irradiation remains an arduous task. Based on this, we designed two types of CQDs, C-CQDs (carboxylic-rich) and A-CQDs (amine-rich) with distinct molecular surfaces. Owing to the higher amount of upward band bending induced by amine-rich molecular surface, A-CQDs efficiently harvest the visible light and prevent recombination kinetics resulting in prolonged lifetimes (25 ps), and augmented charge carrier density (35.7 × 1018) of photoexcited charge carriers. A-CQDs enabled rapid visible-light-driven photolysis of H2O2 (k = 0.058 min-1) and produced higher quantity of •OH radicals (0.158 µmol/sec) for the mineralization of petroleum waste, BETX (i.e. Benzene, Ethylbenzene, Toluene and Xylene) (k = 0.017-0.026 min-1) and real textile wastewater (k = 0.026 min-1). To assess comparative toxicities of both remediated and non-remediated real wastewater samples in a time and dose depended manner, Drosophila melanogaster was used as a model organism. The findings unequivocally demonstrate the potential of remediated wastewater for watering urban forestry.

4.
ACS Appl Mater Interfaces ; 15(42): 49083-49094, 2023 Oct 25.
Artículo en Inglés | MEDLINE | ID: mdl-37819203

RESUMEN

Despite the fact that carbon quantum dots (CQDs) have significant catalytic potential, only emblematic applications that rely on simple acid-base or hydrogen-bonding activation pathways have been reported. In this study, natural amine-targeted CQDs (NAT-CQDs) have been successfully fabricated using a sustainable technique that harnesses a renewable green source. Based on a holistic sustainable assessment, the present approach for the synthesis of NAT-CQDs surpasses previously reported methods in terms of estimated circular and good-manufacturing-practice metrics. A set of spectroscopic and analytical techniques, including FTIR, XPS, conductometric assay, pH titration, 19FNMR, and 13CNMR confirms the presence of the assessable amino-rich groups (0.0083N) at the surface of NAT-CQDs. The occurrence of surface amine groups unlocked the molecular behavior of as-prepared NAT-CQDs and makes them an unprecedented nanoaminocatalytic platform for the synthesis of diverse pharmacophore scaffolds (>40 examples) via a one-pot Knoevenagel/(aza) Michael addition reaction in water at room temperature. The assessable amine group can covalently activate carbonyl groups through nucleophilic iminium activation modes in water and facilitate the ability to build valuable and therapeutic scaffolds on a gram scale. By transferring significant molecular primacy at the frontier of nanoscale materials, NAT-CQDs can thus bridge the gap between the nanoscale and molecular domains. This protocol can also be applied for the preparation of therapeutic anticoagulant drugs, warfarin, and coumachlor. All the reactions exhibited a high atom economy, low E-factor, low process mass intensity (PMI), high reaction mass efficiency (RME), high carbon efficiency (CE), and high catalyst reusability with overall high sustainable values. NAT-CQDs show high recyclability, and the spectral data of reused catalysts indicate that the NAT-CQDs maintained their surface chemistry and electronic properties, suggesting their stability under the tested conditions. This study presents a remarkable instance of NAT-CQDs showcasing covalent catalysis. Expanding on the aforementioned design concept, the utilization of NAT-CQDs' "potential" as distinct colloidal organocatalysts in aqueous environments at the molecular level introduces valuable prospects for aminocatalytic pathways.

5.
Environ Res ; 231(Pt 2): 116181, 2023 08 15.
Artículo en Inglés | MEDLINE | ID: mdl-37207730

RESUMEN

Developing an efficient heterogeneous photocatalyst for environmental remediation and treatment strategies using visible light harvesting processes is promising but challenging. Herein, Cd1-xCuxS materials have been synthesized and characterized by precise analytical tools. Cd1-xCuxS materials exhibited excellent photocatalytic activity for direct Red 23 (DR-23) dye degradation in visible light irradiation. The operational parameters, like dopant concentration, photocatalyst dose, pH, and initial concentration of dye were investigated during the process. The photocatalytic degradation process follows pseudo-first-order kinetics. As compared to other tested materials, 5% Cu doped CdS material revealed superior photocatalytic performance for the degradation of DR-23 (k = 13.96 × 10-3 min-1). Transient absorption spectroscopy, EIS, PL, and transient photocurrent indicated that adding copper to the CdS matrix improved the separation of photo-generated charge carriers by lowering the recombination rate. Spin-trapping experiments recognized the photodegradation primarily based on secondary redox products, i.e., hydroxyl and superoxide radicals. According to by Mott-Schottky curves, photocatalytic mechanism and photo-generated charge carrier density were elucidated regarding dopant-induced valence and conduction bands shifting. Thermodynamic probability of radical formation in line with the altered redox potentials by Cu doping has been discussed in the mechanism. The identification of intermediates by mass spectrometry study also showed a plausible breakdown mechanism for DR-23. Moreover, samples treated with nanophotocatalyst displayed excellent results when tested for water quality metrics such as DO, TDS, BOD, and COD. Developed nanophotocatalyst shows high recyclability with superior heterogeneous nature. 5% Cu-doped CdS also exhibit strong photocatalytic activity for the degradation of colourless pollutant bisphenol A (BPA) under visible light (k = 8.45 × 10-3 min-1). The results of this study offer exciting opportunities to alter semiconductors' electronic band structures for visible-light-induced photocatalytic activity for wastewater treatment.


Asunto(s)
Cobre , Nanoporos , Cobre/química , Cadmio , Especies Reactivas de Oxígeno , Luz , Recombinación Genética , Catálisis
6.
ACS Appl Mater Interfaces ; 15(5): 6970-6981, 2023 Feb 08.
Artículo en Inglés | MEDLINE | ID: mdl-36701196

RESUMEN

Despite the modern boost, developing a new photocatalytic system for the reduction of aldehydes is still challenging due to their high negative reduction potential. Herein, we have used a metal-free photoinduced electron-transfer system based on a cheap and readily available organic dye eosin Y (EY), graphene oxide (GO), and ammonium oxalate (AO) for photocatalytic reduction of structurally diverse aldehydes under sustainable conditions. The protocol shows remarkable selectivity for the photocatalytic reduction of aldehydes over ketones. The decisive interaction of GO and AO with the various states of EY (ground, singlet, triplet, and radical anions), which are responsible for the commencement of the reaction, was examined by various theoretical, optical, electrochemical, and photo-electrochemical studies. The synergetic system of GO, EY, and AO is appropriate for enhancing the separation efficiency of visible-light-induced charge carriers. GO nanosheets act as an electron reservoir to accept and transport photogenerated electrons from the photocatalytic system to the reactant. The reduction of the GO during the process ruled out the back transfer of photoexcited charges. Control experiments explained that the reaction involves two stages: electron transfer and protonation. This process eliminates the necessity of precious-metal-based photocatalysts or detrimental sacrificial agents and overcomes the redox potential limitations for the photoreduction of aldehydes.

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