A compilation of new advances made in the research field of laboratory reaction kinetics in China's Key Development Project for Air Pollution Formation Mechanism and Control Technologies was presented. These advances are grouped into six broad, interrelated categories, including volatile organic compound (VOC) oxidation, secondary organic aerosol (SOA) formation, new particle formation (NPF) and gas-particle partitioning, ozone chemistry, model parameters, and secondary inorganic aerosol (SIA) formation, highlighting the laboratory work done by Chinese researchers. For smog chamber applications, the current knowledge gained from laboratory studies is reviewed, with emphasis on summarizing the oxidation mechanisms of long-chain alkanes, aromatics, alkenes, aldehydes/ketones in the atmosphere, SOA formation from anthropogenic emission sources, and oxidation of aromatics, isoprene, and limonene, as well as SIA formation. For flow tube applications, atmospheric oxidation mechanisms of toluene and methacrolein, SOA formation from limonene oxidation by ozone, gas-particle partitioning of peroxides, and sulfuric acid-water (H2SO4-H2O) binary nucleation, methanesulfonic acid-water (MSA-H2O) binary nucleation, and sulfuric acid-ammonia-water (H2SO4-NH3-H2O) ternary nucleation are discussed.
In-situ catalytic deNOx is a promising NOx control technology for circulating fluidized bed (CFB) boilers. In this application, matching the conditions between the catalyst and gaseous species is crucial. To understand this, a comprehensive computational particle fluid dynamics (CPFD) model was established; flow, combustion, and NOx emission characteristics in an industrial CFB boiler were elaborated; 20 catalysts with various sizes and densities were designed, and their degree of matching with the gaseous species was evaluated. The simulation results indicated that NOx was gradually produced at the bottom of the furnace and attained its maximum concentration at the elevation of secondary air; CO showed a high concentration in the bottom dense-phase zone; and the homogeneous NO-CO reaction is too weak to effectively reduce NOx. With catalyst application, the NO-CO reaction was evidently enhanced and the in-furnace NOx concentration decreased significantly. The 20 evaluated catalysts can be categorized as dipleg deposition, fluidization circulating, furnace suspension, and furnace deposition types. While the last three types of catalysts could match the spatial and temporal distribution of CO and NOx species well, the furnace suspension-type catalyst produced an optimal matching degree and maximum deNOx efficiency.
Unexpected health shocks may bring catastrophic consequences for households. This paper examines the effect of unexpected adverse health shocks on household members' physical and mental health, labor supply, household income and asset, and health behaviors in China by analyzing two nationally representative datasets and adopting a difference-in-differences method augmented with coarsened exact matching. We find that an unexpected health shock results in a discounted out-of-pocket medical expenditure of 16,943 RMB (US$ 2647) over five years for an average household, a reduction of household income per capita of 841 RMB per year (US$ 131, or 6.0% of household annual income per capita), and a loss of net household asset per capita of 13,635 RMB (US$ 2130, or 9.7% of household asset per capita). It raises the probability of an average household applying for public poverty relief allowance by 2.8 percentage points. In addition, we document a strong intra-household spillover effect of health shocks on mental health and health behaviors. A simple back-of-envelope calculation shows that the health shock induces a private cost of 34,966 RMB (US$ 5463) over 5 years for an average household, and incurs a social financial burden of 6066 RMB (US$ 948) in 5 years per household in medical reimbursement and social welfare transfers. At a national scale, the total social burden of health shocks from cardiovascular and cerebrovascular diseases amounts to 1.1 trillion RMB (US$ 172.1 billion) over 5 years.
Achieving efficient degradation of organic pollutants via activation of sulfite is meaningful but challenging. Herein, we have constructed a heterogeneous catalyst system involving Co3O4 and TiO2 nanoparticles to form the p-n heterojunction (Co3O4/TiO2) to degrade acetaminophen (ACE) through photocatalytic activation of sulfite. Specifically, X-ray photoelectron spectroscopy analysis and theoretical calculations provide compelling evidence of electron transfer from Co3O4 to TiO2 at the heterointerface. The interfacial electron redistribution of Co3O4/TiO2 tunes the adsorption energy of HSO3‒/SO32‒ in sulfite activation process for enhanced the catalytic activity. Owing to its unique heterointerface, the degradation efficiency of ACE reached 96.78% within 10 min. The predominant active radicals were identified as •OH, h+, and SOx•− through radical quenching experiments and electron spin resonance capture. Besides, the possible degradation pathway was deduced by monitoring the generated intermediate products. Thereafter, the enhanced roles of well-engineered compositing interface in photocatalytic activation of sulfite for complete degradation of ACE were unveiled that it can improve light absorption ability, facilitate the generation of active species, and optimize reactive pathways. Considering that sulfite is a waste from flue gas desulfurization process, the photocatalytic activation of sulfite system will open up new avenues of beneficial use of air pollutants for the removal of pharmaceutical wastewater.
Implementing the Kigali Amendment to the Montreal Protocol has imposed certain restrictions on the production and consumption of hydrofluorocarbons (HFCs). Taking this opportunity to promote the alternatives of high global warming potential (GWP) HFC refrigerants in the room air conditioner (RAC) sector as well as improve the energy efficiency can bring double benefits. With the RAC sector as an example, a demand-emissions-cost model is developed to assess the potential and costs of emission reductions in different regions of China under different scenarios. The model includes three scenarios: a business as usual (BAU) scenario, a Kigali energy efficiency (KAE) scenario with simultaneous energy efficiency improvements following the Kigali amendment, and an accelerated transition energy efficiency (ATE) scenario with accelerated HFCs reduction and energy efficiency improvements. The results show that under the KAE and ATE scenario, the GHG emissions of the RAC sector will peak in 2025 at 389.8–393.9 Mt CO2-eq and 378.8–382.8 Mt CO2-eq in China. The main contribution to this result is the alternative of low GWP refrigerants. From 2021 to 2060, the cumulative direct emission reductions are about 6.4–7.4 Gt CO2-eq and 8.5–9.5 Gt CO2-eq in KAE and ATE, and the cumulative indirect emission re- ductions for both scenarios are 1.6–1.8 Gt CO2-eq. The cumulative abatement costs are $286–321 billion and $288–322 billion (prices in 2020). Under the ATE scenario, direct emissions from refrigerants in the RAC sector are near zero in 2060, and indirect emissions depend on the power system structure. The RAC sector’s average abatement cost varies significantly in diverse climatic environments. Given the variation in average abatement cost, it is critical to tailor mitigation policies to local conditions to ensure maximum benefits.
The nanoconfinement effect in Fenton-like reactions shows great potential in environmental remediation, but the construction of confinement structure and the corresponding mechanism are rarely elucidated systematically. Herein, we proposed a novel peroxymonosulfate (PMS) activation system employing the single Fe atom supported on mesoporous N-doped carbon (FeSA-MNC, specific surface area = 1520.9 m2/g), which could accelerate the catalytic oxidation process via the surface-confinement effect. The degradation activity of the confined system was remarkably increased by 34.6 times compared to its analogue unconfined system. The generation of almost 100% high-valent iron-oxo species was identified via 18O isotope-labeled experiments, quenching tests, and probe methods. The density functional theory illustrated that the surface-confinement effect narrows the gap between the d-band center and Fermi level of the single Fe atom, which strengthens the charge transfer rate at the reaction interface and reduces the free energy barrier for PMS activation. The surface-confinement system exhibited excellent pollutant degradation efficiency, robust resistance to coexisting matter, and adaptation of a wide pH range (3.0–11.0) and various temperature environments (5–40 °C). Finally, the FeSA-MNC/PMS system could achieve 100% sulfamethoxazole removal without significant performance decline after 10,000-bed volumes. This work provides novel and significant insights into the surface-confinement effect in Fenton-like chemistry and guides the design of superior oxidation systems for environmental remediation.
Solar-driven photosynthesis is a sustainable process for the production of hydrogen peroxide, the efficiency of which is plagued by side reactions. Metal-free covalent organic frameworks (COFs) that can form suitable intermediates and inhibit side reactions show great promise to photo-synthesize H2O2. However, the insufficient formation and separation/transfer of photogenerated charges in such materials restricts the efficiency of H2O2 production. Herein, we provide a strategy for the design of donor-acceptor COFs to greatly boost H2O2 photosynthesis. We demonstrate that the optimal intramolecular polarity of COFs, achieved by using suitable amounts of phenyl groups as electron donors, can maximize the free charge generation, which leads to high H2O2 yield rates (605 μmol g−1 h−1) from water, oxygen and visible light without sacrificial agents. Combining in-situ characterization with computational calculations, we describe how the triazine N-sites with optimal N 2p states play a crucial role in H2O activation and selective oxidation into H2O2. We further experimentally demonstrate that H2O2 can be efficiently produced in tap, river or sea water with natural sunlight and air for water decontamination.
The ultra-low NOx emission requirement (50 mg/m3) brings great challenge to CFB boilers in China. To further tap the NOx abatement potential, full understanding the fundamentals behind CFB boilers is needed. To achieve this, a comprehensive CPFD model is established and verified; gas-solid flow, combustion, and NOx emission behavior in an industrial CFB boiler are elaborated; influences of primary air volume and coal particle size on furnace performance are evaluated. Simulation results indicate that there exists a typical core-annular flow structure in the boiler furnace. Furnace temperature is highest in the bottom dense-phase zone (about 950 °C) and decreases gradually along the furnace height. Oxygen-deficient combustion results in high CO concentration and strong reducing atmosphere in the lower furnace. NOx concentration gradually increases in the bottom furnace, reaches maximum at the elevation of secondary air inlet, and then decreases slightly in the upper furnace. Appropriate decreasing the primary air volume and coal particle size would increase the CO concentration and intensify the in-furnace reducing atmosphere, which favors for NOx reduction and low NOx emission from CFB boilers.
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.
