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As a promising environmental remediation technology, the electro-Fenton (EF) process is mainly limited by the two rate-limiting steps, which are H2O2 generation and activation. The electrocatalytic three-electron oxygen reduction reaction (3e- ORR) can directly activate oxygen to hydroxyl radicals (â¢OH), which is expected to break through the rate-limiting steps of the EF process. However, limited success has been achieved in the design of 3e- ORR electrocatalysts. Herein, we propose Cu/CoSe2/C with the strong metal-support interactions to enhance the 3e- ORR process, exhibiting remarkable reactivity and stability for â¢OH generation. Both experiment and DFT calculation results reveal that CoSe2 is conducive to the generation of H2O2. Meanwhile, the metallic Cu can enhance the adsorption strength of *H2O2 intermediates and thus promotes the one-electron reduction to â¢OH. The Cu/CoSe2/C catalyst exhibits the electron-transfer number close to 3.0 during the ORR process, and exhibits the outstanding â¢OH generation performance, achieving a higher apparent rate constant (6.0 times faster) toward ciprofloxacin compared with its analogy without the SMSI effect. Our work represents that the SMSI effect endows Cu/CoSe2/C high activity and selectivity for â¢OH generation, providing a unique perspective for the design of a high-efficiency 3e- ORR catalyst.
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Two-electron oxygen reduction reaction (2e- ORR) is a promising method for the synthesis of hydrogen peroxide (H2O2). However, high energy barriers for the generation of key *OOH intermediates hinder the process of 2e- ORR. Herein, we prepared a copper-supported indium selenide catalyst (Cu/In2Se3) to enhance the selectivity and yield of 2e- ORR by employing an electronic metal-support interactions (EMSIs) strategy. EMSIs-induced charge rearrangement between metallic Cu and In2Se3 is conducive to *OOH intermediate generation, promoting H2O2 production. Theoretical investigations reveal that the inclusion of Cu significantly lowers the energy barrier of the 2e- ORR intermediate and impedes the 4e- ORR pathway, thus favoring the formation of H2O2. The concentration of H2O2 produced by Cu/In2Se3 is ~2â times than In2Se3, and Cu/In2Se3 shows promising applications in antibiotic degradation. This research presents a valuable approach for the future utilization of EMSIs in 2e- ORR.
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Heterogeneous electro-Fenton (HEF) process has been regarded as a promising method in environmental remediation. However, the reaction kinetic mechanism of the HEF catalyst for simultaneous production and activation of H2O2 remained confounded. Herein, the copper supported on polydopamine (Cu/C) was synthesized by a facile method and employed as a bifunctional HEFcatalyst, and the catalytic kinetic pathways were deeply investigated by using rotating ring-disk electrode (RRDE) voltammetry based on the Damjanovic model. Experimental results substantiated that a two-electron oxygen reduction reaction (2e- ORR) and a sequential Fenton oxidation reaction were proceeded on 1.0-Cu/C, where metallic copper played a crucial role in the fabrication of 2e- active sites as well as utmost H2O2 activation to produce highly reactive oxygen species (ROS), resulting in the high H2O2 productivity (52.2%) and the almost complete removal of contaminant ciprofloxacin (CIP) after 90 min. The work not only expanded the idea of reaction mechanism on Cu-based catalyst in HEF process but also provided a promising catalyst for pollutants degradation in wastewater treatment.
Assuntos
Cobre , Poluentes Químicos da Água , Cobre/química , Peróxido de Hidrogênio/química , Poluentes Químicos da Água/análise , Indóis , Catálise , Oxirredução , EletrodosRESUMO
Designing catalysts that can effectively activate oxygen and hydrogen peroxide is a huge challenge in electro-Fenton (EF) process. Considering the superior ability of electrons transport and activation of H2O2, ceria encapsulated with N, P-codoped carbon material was a promising catalyst for EF reaction. Herein, CeO2-NPCTX (where T and X represented the calcination temperature and the initial mass of CeO2, respectively) materials were synthesized via pyrolysis process and used as catalysts to degrade ciprofloxacin (CIP) in EF process. The results indicated that CeO2-NPC1000100 catalyst had good degradation performance under the optimal conditions. Compared with CeO2 and CeO2-NC1000100 catalysts, CeO2-NPC1000100 catalyst had more content of graphite N and more oxygen vacancies, which were beneficial to activation of oxygen and hydrogen peroxide. Scavenging experiments and electron paramagnetic resonance analysis confirmed ·O2- and ·OH were the main reactive oxygen species in the CIP degradation process. And three logical degradation routes of CIP were given. In addition, CeO2-NPC1000100 catalyst still had good stability after three times of continuous operation, and presented good universality for the treatment of a variety of antibiotic wastewaters. Finally, a convincing mechanism in the EF system with CeO2-NPC1000100 for CIP degradation was proposed.
Assuntos
Peróxido de Hidrogênio , Poluentes Químicos da Água , Carbono , Catálise , Elétrons , Oxirredução , Poluentes Químicos da Água/análiseRESUMO
Tetrathiafulvalene (TTF) was successfully applied to degrade rhodamine 6G (Rh6G) in photocatalytic system. The results exhibited that TTF had excellent suitability in the range of weak acid to weak base (pH = 5-9). Multiple reactive oxygen species (ËOH, 1O2, H2O2 and ËO2-) as well as h+ and e- were generated in photocatalytic process, causing the rapid degradation of Rh6G. This study provides new ideas for the development of catalysts in photocatalytic system and the broader applications of organic semiconductor materials.
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Due to environmentally friendly operation and on-site productivity, electrocatalytic singlet oxygen (1O2) production via O2 gas is of immense interest in environment purification. However, the side-on configuration of O2 on the catalysts surface will lead to the formation of H2O, which seriously limits the selectivity and activity of 1O2 production. Herein, we show a robust N-doped CuO (N-CuO) with Pauling-type (end-on) adsorption of O2 at the N-Cu-O3 sites for the selective generation of 1O2 under direct-current electric field. We propose that Pauling-type configuration of O2 not only lowers the overall activation energy barrier, but also alters the reaction pathway to form 1O2 instead of H2O, which is the key feature determining selectivity for the dissociation of Cu-O bonds rather than the O-O bonds. The proposed N dopant strategy is applicable to a series of transition metal oxides, providing a universal electrocatalysts design scheme for existing high-performance electrocatalytic 1O2 production.
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The residual ciprofloxacin (CIP) in water seriously menaces the ecological safety and public health. Here, a Fe-free photo-electro-Fenton-like (PEF) system was designed for efficient degradation of CIP in water. A Z-scheme MnOx/g-C3N4 (MCN) nanocomposite with low-cost, large specific surface area and abundant active sites was successfully synthesized as a photoelectric catalyst. The XPS analysis indicated the presence of Mn2+, Mn3+ and Mn4+ in the MCN (1:6) composite, and the conversion among polyvalent manganese made the decomposition of H2O2 more efficient. Therefore, the manganese ions replaced the Fe element in traditional Fenton system. With the MCN (1:6), the PEF system could also produce O2-, OH and h+ under the visible light irradiation. The synergetic excitation of multiple active species promoted the rapid decomposition of CIP. Besides, the polyvalent property of manganese oxide resulted in the presence of oxygen vacancies which could improve the electrocatalytic reactivity of the catalyst. Finally, the degradation efficiency of CIP was 96.23% in 120 min and the mineralization efficiency was 80.02% in 240 min.
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Ciprofloxacina , Poluentes Químicos da Água , Peróxido de Hidrogênio , Ferro , Manganês , Oxirredução , Poluentes Químicos da Água/análiseRESUMO
Iliac atherosclerosis is common in renal transplant recipients. In severe cases, it affects intraoperative renal arterial anastomosis and increases the risk of postanastomosis complications. At present, safe and efficient vascular replacement methods are relatively limited. In the 2 renal transplant cases at our center, described here, the donors' iliac arteries were unavailable. We therefore attempted to replace the recipients' diseased external iliac artery with the donors' inferior vena cava and then performed an end-to-side grafting with the attachment in arterial reconstruction. One patient received a single kidney transplantation, while the other received a dual kidney transplantation. Antiplatelet/anticoagulation drug application was avoided, and both patients were observed for more than 6 months. Stable renal graft function was achieved without any vascular complications. During this study, all procedures were in compliance with the Helsinki Congress and the Declaration of Istanbul. For end-stage renal disease patients with severe iliac atherosclerosis who are waiting for kidney transplantation, a donor's vena cava graft could potentially be a promising replacement option to restore external iliac artery patency and reconstruct renal blood flow, without the necessity of harvesting a recipient's autologous vessels or looking for costly artificial ones.
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Aterosclerose/cirurgia , Artéria Ilíaca/cirurgia , Transplante de Rim/métodos , Enxerto Vascular/métodos , Veia Cava Inferior/transplante , Aterosclerose/etiologia , Humanos , Artéria Ilíaca/patologia , Rim/irrigação sanguínea , Falência Renal Crônica/complicações , Falência Renal Crônica/cirurgia , Masculino , Pessoa de Meia-IdadeRESUMO
Coronavirus disease 2019 (COVID-19) is a novel and lethal infectious disease, posing a threat to global health security. The number of cases has increased rapidly, but no data concerning kidney transplant (KTx) recipients infected with COVID-19 are available. To present the epidemiological, clinical, and therapeutic characteristics of KTx recipients infected with COVID-19, we report on a case series of five patients who were confirmed as having COVID-19 through nucleic acid testing (NAT) from January 1, 2020 to February 28, 2020. The most common symptoms on admission to hospital were fever (five patients, 100%), cough (five patients, 100%), myalgia or fatigue (three patients, 60%), and sputum production (three patients, 60%); serum creatinine or urea nitrogen levels were slightly higher than those before symptom onset. Four patients received a reduced dose of maintenance immunosuppressive therapy during hospitalization. As of March 4, 2020 NAT was negative for COVID-19 in three patients twice in succession, and their computed tomography scans showed improved images. Although greater patient numbers and long-term follow-up data are needed, our series demonstrates that mild COVID-19 infection in KTx recipients can be managed using symptomatic support therapy combined with adjusted maintenance immunosuppressive therapy.
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Betacoronavirus/isolamento & purificação , Técnicas de Laboratório Clínico , Infecções por Coronavirus/diagnóstico , Imunossupressores/efeitos adversos , Transplante de Rim/efeitos adversos , Infecções Oportunistas/diagnóstico , Pneumonia Viral/diagnóstico , Transplantados , Adulto , Betacoronavirus/genética , Betacoronavirus/imunologia , COVID-19 , Teste para COVID-19 , China , Infecções por Coronavirus/terapia , Infecções por Coronavirus/virologia , Feminino , Humanos , Hospedeiro Imunocomprometido , Imunossupressores/administração & dosagem , Masculino , Pessoa de Meia-Idade , Infecções Oportunistas/terapia , Infecções Oportunistas/virologia , Pandemias , Pneumonia Viral/terapia , Pneumonia Viral/virologia , Valor Preditivo dos Testes , SARS-CoV-2 , Índice de Gravidade de Doença , Fatores de Tempo , Resultado do TratamentoRESUMO
Polyacrylamide (PAM) in environmental water has become a major problem in water pollution management due to its high molecular mass, corrosion resistance, high viscosity, and nonabsorption by soil. The composite of Fe-doped Ce0.75Zr0.25O2 solid solution (Fe-Ce0.75Zr0.25O2) loaded on carbon felt (CF) was fabricated by a hydrothermal synthesis method, which was used as the cathode in a heterogeneous electro-Fenton system for the degradation of PAM. It showed that the degradation efficiency of PAM by the Fe-Ce0.75Zr0.25O2/CF cathode was 86% after 120 min and the molecular mass of PAM decreased by more than 90% after 300 min. Total organic carbon removal reached 78.86% in the presence of Fe-Ce0.75Zr0.25O2/CF, while the value was only 38.01% in the absence of Fe-Ce0.75Zr0.25O2. Further studies showed that the breaking of the chain begins with the amide bond, and then, the carbon chain was cracked into a short alkyl chain. As degradation progressed, both the complex viscosity and elasticity modulus of PAM solutions decreased nearly 50% at 300 min. It indicated that â¢OH were the most significant active species for the degradation of PAM. This novel Fe-Ce0.75Zr0.25O2/CF composite is an efficient and promising electrode for the removal of PAM in wastewater.