Growing national decarbonization commitments require rapid and deep reductions of carbon dioxide emissions from existing fossil-fuel power plants. Although retrofitting existing plants with carbon capture and storage or biomass has been discussed extensively, yet such options have failed to provide evident emission reductions at a global scale so far. Assessments of decarbonization technologies tend to focus on one specific option but omit its interactions with competing technologies and related sectors (e.g., water, food, and land use). Energy system models could mimic such inter-technological and inter-sectoral competition but often aggregate plant-level parameters without validation, as well as fleet-level inputs with large variability and uncertainty. To enhance the accuracy and reliability of top-down optimization models, bottom-up plant-level experience accumulation is of vital importance. Identifying sweet spots for plant-level pilot projects, overcoming the technical, financial, and social obstacles of early large-scale demonstration projects, incorporating equity into the transition, propagating the plant-level potential to generate fleet-level impacts represent some key complexity of existing fossil-fuel power plant decarbonization challenges that imposes the need for a serious re-evaluation of existing fossil fuel power plant abatement in energy transition.
Photocatalytic efficiency toward volatile organic compounds (VOCs) decomposition has crucially relied on the nature of their stereochemical structures, in which the complicated decomposition mechanism has not been unveiled. As typical cases of VOCs pollutants, m-, p-, and o-xylene isomers share the identical molecular formula with discrepant methyl positions at the benzene ring. The essential contribution of the methyl position to the decomposition mechanism of xylene isomers, especially the rate-determining step for benzene ring-opening, is unraveled in this work. It is identified that the decomposition rate of xylene isomers on the SnO2 catalyst is decreased in the order of o-xylene > m-xylene ≈ p-xylene. The durability of SnO2 photocatalyst is also accomplished for a superior o-xylene decomposition performance. By combining the experimental and theoretical investigation, it is manifested that the regulation of methyl positions in the ortho-sites is an appealing route for reducing the ring-opening energy barriers and guiding the complete mineralization of the hazardous xylene. This work could provide insights into unraveling the unique role of the stereochemical structure of xylene on ring-opening barriers for efficient and stable VOC decomposition.
The massive use of antibiotics has led to their omnipresence in aquatic environments, and the photodegradation was found to be the dominant transformation process for antibiotics in the natural river system. Herein, we investigated the photodegradation kinetics of 77 antibiotics in 7 classes in water under simulated sunlight. Using the quantum chemical descriptors predicted by the density functional theory calculation, the quantitative structure-activity relationship (QSAR) models were established to explore the main chemical descriptors determining the photodegradation of antibiotics. The results showed that the photodegradation kinetics of antibiotics conformed to the pseudo-first order kinetic model. The photodegradation rate constants of different antibiotics varied 4 orders of magnitude, and the photodegradation rate constants of quinolones were significantly higher than those for other classes of antibiotics due to the F atoms in their molecular structures. The developed QSAR models revealed that the energy gap (Egap) between ELUMO and EHOMO was the main chemical descriptor determining the photodegradation of antibiotics, and it was negatively correlated with lgk. In addition, the number of F atom was also included in the QSAR models due to the great contribution of F atom to the direct photolysis of quinolones. This study ordered the photodegradation rate constants of 77 antibiotics, and revealed the major chemical descriptors determining the photodegradation of antibiotics. The results provide the basic information for the photolysis of antibiotics, which is significant for predicting the environmental behaviors and evaluating the ecological risks of antibiotics in aquatic environments.
Though metal resistance genes (MRGs) are of global concern in aquatic ecosystems, the underlying factors responsible for MRGs dissemination, especially in urban rivers on the vulnerable Qinghai-Tibet Plateau, are rarely known. Here, we collected 64 samples including water and sediments during the wet and dry seasons and effluents from six wastewater treatment plants (WWTPs) during the dry season and measured 50 metal(loid)s, 60 bacterial phyla, and 259 MRGs. We observed the distinct difference of metal(loid)s, bacterial communities, and MRGs between water and sediments and the great seasonal changes in metal(loid)s and bacterial communities instead of MRGs. Thirty-one metal(loid)s were detectable in the water, with relatively low concentrations and no significant effects on the planktonic bacterial communities and MRGs. Interestingly, the WWTPs effluent partially promoted the prevalence of dissolved metal(loid)s, bacterial communities, and MRGs along the river. In the sediments, the average concentrations of 17 metal(loid)s exceeded their corresponding background levels in this region and strongly influenced the bacterial communities and the MRGs. Sedimentary Hg and Cd, mainly sourced from the intensive animal husbandry, were the major pollutants causing ecological risks and largely shaped their corresponding resistomes. Moreover, we found that bacterial communities predominantly determined the variation of MRGs in both water and sediments. Metagenome-assembled genomes further reveals the widespread co-occurrence of MRGs and antibiotic resistance genes (ARGs) in MRG hosts. Our study highlighted the concern of effluents discharged from WWTPs and emphasized the importance of controlling the anthropogenic inputs of sedimentary metal(loid)s in the plateau river ecosystems.
Vacuum triodes have been scaled down to the microscale on a chip by microfabrication technologies to be vacuum transistors. Most of the reported devices are based on field electron emission, which suffer from the problems of unstable electron emission, poor uniformity, and high requirement for operating vacuum. Here, to overcome these problems, a vacuum transistor based on Field-Assisted thermionic emission from individual carbon nanotubes is proposed and fabricated using microfabrication technologies. The carbon nanotube vacuum transistor exhibits an ON/OFF current ratio as high as 104 and a subthreshold slope of 4 V·dec−1. The gate controllability is found to be strongly dependent on the distance between the collector electrodes and electron emitter, and a device with the distance of 1.5 μm shows a better gate controllability than that with the distance of 0.5 μm. Benefiting from Field-Assisted thermionic emission mechanism, electric field required in our devices is about one order of magnitude smaller than that in the devices based on field electron emission, and the surface of the emitters shows much less gas molecule absorption than cold field emitters. These are expected to be helpful for improving the stability and uniformity of the devices.
In this study, vanadium trioxide (V2O3) was adopted to activate PMS via a Fenton-like reaction to degrade metronidazole (MNZ). The V2O3-PMS system can almost completely degrade MNZ at 30 min with 42.4% TOC removal. Comparative tests reveal that V2O3 stands out among a variety of heterogeneous catalysts, including metallic oxides and carbon materials. Sulfate radicals (SO4•−) and hydroxyl radicals (•OH) derived from PMS decomposition are major reactive oxygen species, based on quenching tests, electron spin resonance (ESR) analysis, the steady-state concentrations of radicals ([SO4•−]ss = 5.1 × 10-13 M and [•OH]ss = 4.0 × 10-14 M), and kinetics model. The process of stepwise electron transfer from vanadium species to PMS to produce reactive radicals was proved by small-molecule simulation experiments and pickling experiments of vanadium oxides. Possible pathways of MNZ degradation were proposed based on the results of LC-MS and Fukui function, including two stages of the hydroxylation and bond cleavage of nitro and the subsequent ring-opening. This study reveals the high reusability and practicability of the V2O3-PMS system over a relatively wide pH range, which puts forward a new vision on V2O3 induced Fenton-like reactions and a new reference method for the removal of medical organic contaminants in water.