科研成果

Persulfate-based advanced oxidation processes (AOPs) have obtained increasing attention due to the generation of sulfate radical (SO4•‒) with high reactivity for organic contaminants degradation. Numerous activation methods have been used to activate two common persulfates: peroxymonosulfate (PMS) and peroxydisulfate (PDS). However, the comparisons of activation methods and two oxidants in the comprehensive degradation performance of the target contaminant are still limited. Thus, taking norfloxacin (NOR) as the target contaminant, we proposed five key parameters (the observed pseudo-first-order rate constant, kobs; average mineralization rate, rm; utilization efficiency of catalyst, Ucat; utilization efficiency of oxidant, Uox; and net utilization efficiency of oxidant, Uox’) to quantify the comprehensive degradation performance of NOR. The irradiation affected target pollutants, catalysts, and oxidants, leading to an improved degradation performance of NOR. Various heterogeneous catalysts were compared in terms of the key elements contained. Fe, Co, and Mn-based materials performed better, while carbon-based catalysts performed poorly on NOR degradation. The overall degradation performance of NOR was different for PMS and PDS, which can be ascribed to their varied reaction pathways towards NOR, but stemmed from different properties of PMS and PDS. Besides, the effect of pH on the degradation efficiency of NOR was investigated. A neutral solution was optimal for PMS system, while an acidic solution worked better for PDS system. Finally, we analyzed the molecule structure of NOR by density functional theory (DFT) calculation to study the sites easy to attack. Then, we summarized four typical degradation pathways of NOR in SO4•‒-based AOP systems, including defluorination, piperazine ring cleavage, piperazine ring oxidation, and quinoline group transformation.

Singlet oxygen (1O2) plays a crucial role in Fenton-like reactions due to its high efficiency and selectivity in removing trace organic pollutants from complex water matrices. Defect engineering, which allows the efficient exposure of active sites and optimization of electronic structures, has rapidly emerged as a fundamental strategy for enhancing 1O2 yield. Herein, we introduce tunable sulfur vacancy (VS) density into Co9S8 catalysts for peroxymonosulfate (PMS) activation. The modulation of the octahedral Co (CoS6) and tetrahedral Co (CoS4) electronic structures by VS triggers the unexpected selective generation of 1O2. The VS/PMS system exhibits excellent resistance to interference and highly selective degradation of electron-donating organic pollutants. Experimental and theoretical calculations revealed a new evolutionary route for 1O2 involving two phases (Phase I: HSO5− → *O, Phase II: *O + HSO5− →*OO → 1O2). This study provides a molecular-level understanding of VS-mediated catalytic selectivity for high-efficient decontamination applications.

In this work, the different selectivity of SO4•- and •OH towards municipal solid waste incineration leachates (MSWILs) was studied by a comparative study of UV/persulfate (PS) and UV/H2O2. Results showed SO4•- preferentially mineralized carbon atoms of higher average oxidation state, while •OH showed a two-stage mechanism of partial oxidation and mineralization successively. Electron spin resonance (ESR) analysis showed SO4•- had superior selectivity towards MSWILs than •OH, and Fe(II) would significantly affect the selectivity via forming Fe-MSWILs complex. As the consequence, Fe(II) showed slightly negative effect on UV/PS, but greatly enhanced the performance of UV/H2O2/Fe(II). High concentration of Cl- affected the degradation of non-fluorescent substances by UV/PS, while SO42- and NO3- showed no effect. In contrast, anions showed no effect on UV/H2O2. In addition, •OH preferentially attacked large molecules, but SO4•- showed no selectivity. This study further revealed the selectivity of SO4•- and •OH in the treatment of hypersaline wastewater, and provided theoretical support for the development of targeted technology.

Abstract We present a novel and effective photocatalytic method for the methylation of ?-diketones with controllable degrees of deuterium incorporation via development of new methyl sources. By utilizing a methylamine-water system as the methyl precursor and a cascade assembly strategy for deuteration degree control, we synthesized methylated compounds with varying degrees of deuterium incorporation, showcasing the versatility of this approach. We examined a range of ?-diketone substrates and synthesized key intermediates for drug and bioactive compounds with varying degrees of deuterium incorporation, ranging from 0 to 3. We also investigated and discussed the postulated reaction pathway. This work demonstrates the utility of readily available reagents, methylamines and water, as a new methyl source, and provides a simple and efficient strategy for the synthesis of degree-controllable deuterium-labelled compounds.

Hydroxyl radical (•OH) and sulfate radical (SO4•−) produced in advanced oxidation processes (AOPs) have been widely studied for organic contaminants degradation, however, the different radical characteristics and reaction mechanisms on organics degradation are still needed. In this study, a homogeneous Co(II)/peroxymonosulfate activation system was established for caffeine (CAF) degradation, and pH was controlled to regulate the radicals production. The different attack routes driven by SO4•− and •OH were deeply explored by transformation products (TPs) identification and theoretical calculations. Specifically, a method on dynamic electronic structure analysis of reactants (R), transition state (TS) and intermediates (IMs) during reaction was proposed, which was applied to elucidate the underlying mechanism of CAF oxidation by •OH and SO4•− at the molecular orbital level. In total, SO4•− is kinetically more likely to attack CAF than •OH due to its higher oxidation potential and electrophilicity index. Single electron transfer reaction (SET) is only favorable for SO4•−due to its higher electron affinity than •OH, while only •OH can react with CAF via hydrogen atom abstraction (HAA) route. Radical adduct formation (RAF) is the most favorable route for both •OH and SO4•− attack according to both kinetics and thermodynamics results. These findings can significantly promote the understanding on the degradation mechanism of organic pollutants driven by •OH and SO4•− in AOPs.

This paper reviews current progress and future challenges of digital technology applications for energy system transition in the context of net-zero. A list of case studies for such digitization enabled optimal design and operation of energy systems at various temporal and spatial scales are reviewed in the paper, including model predictive control, enterprise-wide optimization, eco-industrial park data management, and smart city. The key technological innovations across these applications, such as virtual representation of physical entities, ontological knowledge base, data-driven high dimensional surrogate model based parameterization are also inspected in the paper. Future challenges in terms of data privacy and security are also discussed as potential barriers for digitalization enabled net-zero energy system transition.