Influence of preparation methods on the physicochemical properties and catalytic performance of MnO_x-CeO_2 catalysts for NH_3-SCR at low temperature

This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.

Improving the denitration performance and K-poisoning resistance of the V_2O_5-WO_3/TiO_2 catalyst by Ce^(4+) and Zr^(4+) co-doping

A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐WO3/TiO2 catalyst.The physicochemical properties were investigated by using XRD,BET,NH3‐TPD,H2‐TPR,and XPS,and the catalytic performance and K‐poisoning resistance were evaluated via a NH3‐SCR model reaction.Ce^4+and Zr^4+co‐doping were found to enhance the conversion of NOx,and exhibit the best K‐poisoning resistance owing to the largest BET‐specific surface area,pore volume,and total acid site concentration,as well as the minimal effects on the surface acidity and redox ability from K poisoning.The V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst also presents outstanding H2O+SO2 tolerance.Finally,the in situ DRIFTS reveals that the NH3‐SCR reaction over the V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst follows an L‐H mechanism,and that K poisoning does not change the reaction mechanism.

Support effect of the supported ceria-based catalysts during NH_3-SCR reaction

To investigate how the physicochemical properties and NH3‐selective catalytic reduction(NH3‐SCR)performance of supported ceria‐based catalysts are influenced as a function of support type,a series of CeO2/SiO2,CeO2/γ‐Al2O3,CeO2/ZrO2,and CeO2/TiO2catalysts were prepared.The physicochemical properties were probed by means of X‐ray diffraction,Raman spectroscopy,Brunauer‐Emmett‐Teller surface area measurements,X‐ray photoelectron spectroscopy,H2‐temperature programmed reduction,and NH3‐temperature programmed desorption.Furthermore,the supported ceria‐based catalysts'catalytic performance and H2O+SO2tolerance were evaluated by the NH3‐SCR model reaction.The results indicate that out of the supported ceria‐based catalysts studied,the CeO2/γ‐Al2O3catalyst exhibits the highest catalytic activity as a result of having a high relative Ce3+/Ce4+ratio,optimum reduction behavior,and the largest total acid site concentration.Finally,the CeO2/γ‐Al2O3catalyst also presents excellent H2O+SO2tolerance during the NH3‐SCR process.

Doping effect of cations(Zr^(4+),Al^(3+),and Si^(4+)) on MnO_x/CeO_2 nano-rod catalyst for NH_3-SCR reaction at low temperature

Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods were used as supports to prepare MnOx/CeO2‐NR, MnOx/CZ‐NR, MnOx/CA‐NR, and MnOx/CS‐NR catalysts, respectively. The prepared supports and catalysts were comprehensively characterized by transmission electron microscopy (TEM), high‐resolution TEM, X‐ray diffraction, Raman and N2‐physisorption analyses, hydrogen temperature‐programmed reduction, ammonia temperature‐programmed desorption, in situ diffuse reflectance infrared Fourier‐transform spectroscopic analysis of the NH3 adsorption, and X‐ray photoelectron spectroscopy. Moreover, the catalytic performance and H2O+SO2 tolerance of these samples were evaluated through NH3‐selective catalytic reduction (NH3‐SCR) in the absence or presence of H2O and SO2. The obtained results show that the MnOx/CS‐NR catalyst exhibits the highest NOx conversion and the lowest N2O concentration, which result from the largest number of oxygen vacancies and acid sites, the highest Mn4+ content, and the lowest redox ability. The MnOx/CS‐NR catalyst also presents excellent resistance to H2O and SO2. All of these phenomena suggest that Si4+ is the optimal dopant for the MnOx/CeO2‐NR catalyst.

Data augmentation for bias correction in mapping PM_(2.5) based on satellite retrievals and ground observations

As most air quality monitoring sites are in urban areas worldwide,machine learning models may produce substantial estimation bias in rural areas when deriving spatiotemporal distributions of air pollutants.The bias stems from the issue of dataset shift,as the density distributions of predictor variables differ greatly between urban and rural areas.We propose a data-augmentation approach based on the multiple imputation by chained equations(MICE-DA)to remedy the dataset shift problem.Compared with the benchmark models,MICE-DA exhibits superior predictive performance in deriving the spatiotemporal distributions of hourly PM2.5 in the megacity(Chengdu)at the foot of the Tibetan Plateau,especially for correcting the estimation bias,with the mean bias decreasing from-3.4µg/m3 to-1.6µg/m3.As a complement to the holdout validation,the semi-variance results show that MICE-DA decently preserves the spatial autocorrelation pattern of PM2.5 over the study area.The essence of MICE-DA is strengthening the correlation between PM2.5 and aerosol optical depth(AOD)during the data augmentation.Consequently,the importance of AOD is largely enhanced for predicting PM2.5,and the summed relative importance value of the two satellite-retrieved AOD variables increases from 5.5%to 18.4%.This study resolved the puzzle that AOD exhibited relatively lower importance in local or regional studies.The results of this study can advance the utilization of satellite remote sensing in modeling air quality while drawing more attention to the common dataset shift problem in data-driven environmental research.

Chemical characteristics of long-term acid rain and its impact on lake water chemistry:A case study in Southwest China

The chemical composition of acid rain and its impact on lake water chemistry in Chongqing,China,from 2000 to 2020 were studied in this study.The regional acid rain intensity is affected jointly by the acid gas emissions and the neutralization of alkaline substances.The pH of precipitation experienced three stages of fluctuating decline,continuous improvement,and a slight correction.Precipitation pH showed inflection points in 2010,mainly due to the total control actions of SO_(2)and NO_(x)implemented in 2011.The total ion concentrations in rural areas and urban areas were 489.08μeq/L and 618.57μeq/L,respectively.The top four ions were SO_(4)^(2-),Ca^(2+),NH_(4)^(+)and NO_(3)^(-),which accounted for more than 90%of the total ion concentration,indicating the anthropogenic effects.Before 2010,SO_(4)^(2-)fluctuated greatly while NO_(3)^(-)continued to rise;however,after 2010,both SO_(4)^(2-)and NO_(3)^(-)began to decline rapidly,with the rates of-12.03μeq/(L·year)and-4.11μeq/(L·year).Because the decline rate of SO_(4)^(2-)was 2.91 times that of NO_(3)^(-),the regional acid rain has changed from sulfuric acid rain to mixed sulfuric and nitric acid rain.The lake water is weakly acidic,with an average pH of 5.86,and the acidification frequency is 30.00%.Acidification of lake water is jointly affected by acid deposition and acid neutralization capacity of lake water.Acid deposition has a profound impact on water acidification,and nitrogen(N)deposition,especially reduced N deposition,should be the focus of future research.

An observed nocturnal ozone transport event in the Sichuan Basin,Southwestern China

The ozone(O_(3))pollution in China drew lots of attention in recent years,and the Sichuan Basin(SCB)was one of the regions confronting worsening O_(3)pollution problem.Many previous studies have shown that regional transport is an important contributor to O_(3)pollution.However,very few features of the O_(3)profile during transport have been reported,especially in the border regions between different administrative divisions.In this study,we conducted tethered balloon soundings in SCB during the summer of 2020 and captured a nocturnal O_(3)transport event during the campaign.Vertically,the O_(3)transport occurred in the bottom of the residual layer,between 200 and 500 m above ground level.Horizontally,the transport pathway was directed from southeast to northwest based on the analysis of the wind field and air mass trajectories.The effect of transport in the residual layer on the surface O_(3)concentration was related to the spatial distribution of O_(3).For cities with high O_(3)concentrations in the upwind region,the transport process would bring clean air masses and abate pollution.For downwind lightly polluted cities,the transport process would slow down the decreasing or even increase the surface O_(3)concentration during the night.We provided observational facts on the profile features of a transboundary O_(3)transport event between two provincial administrative divisions,which implicated the importance of joint prevention and control measures.However,the sounding parameters were limited and the quantitative analysis was preliminary,more integrated,and thorough studies of this topic were called for in the future.

Biogenic volatile organic compounds dominated the near-surface ozone generation in Sichuan Basin,China,during fall and wintertime

The complex air pollution driven by both Ozone(O_(3))and fine particulate matter(PM2.5)sig nificantly influences the air quality in the Sichuan Basin(SCB).Understanding the O_(3)for mation during autumn and winter is necessary to understand the atmospheric oxidative capacity.Therefore,continuous in-site field observations were carried out during the late summer,early autumn and winter of 2020 in a rural area of Chongqing.The total volatile organic compounds(VOCs)concentration reported by a Proton-Transfer-Reaction Time-of Flight Mass Spectrometry(PTR-ToF-MS)were 13.66±9.75 ppb,5.50±2.64 ppb,and 9.41±5.11 ppb in late summer,early autumn and winter,respectively.The anthropogenic VOCs(AVOCs)and biogenic VOCs(BVOCs)were 8.48±7.92 ppb and 5.18±2.99 ppb in late sum mer,3.31±1.89 ppb and 2.19±0.93 ppb in autumn,and 6.22±3.99 ppb and 3.20±1.27ppb in winter.A zero-dimensional atmospheric box model was employed to investigate the sensitivity of O_(3)-precursors by relative incremental reactivity(RIR).The RIR values of AV OCs,BVOCs,carbon monoxide(CO),and nitrogen oxides(NOx)were 0.31,0.71,0.09,and-0.36 for late summer,0.24,0.59,0.22,and-0.38 for early autumn,and 0.30,0.64,0.33 and-0.70 for winter,and the results showed that the O_(3)formation of sampling area was in the VOC-limited region,and O_(3)was most sensitive to BVOCs(with highest RIR values,>0.6)This study can be helpful in understanding O_(3)formation and interpreting the secondary formation of aerosols in the winter.

Exhaust emission inventory of typical construction machinery and its contribution to atmospheric pollutants in Chengdu, China

To study the emission characteristics of typical construction machinery in Chengdu,12 construction machinery (excavators,bulldozers,loaders,and forklifts) under idling mode,moving mode,and working mode,were tested using a portable emission measurement system(PEMS).Under three operating modes,the typical construction machinery in the working mode was higher in the fuel-based average emission factors of PM_(2.5)and NOx,while the fuel-based average emission factors of HC and CO were higher in idling mode.Integrated the results of investigation on ownership and activity levels of construction machinery,an exhaust emission inventory of typical construction machinery of Chengdu in 2018 was established according to the recommendation method.The annual emission of PM_(2.5),NOx,HC,and CO were 1.67×106,1.61×108,3.83×106,and 1.26×107kg,respectively,and the excavator contributed the maximum emissions,accounting for an average proportion of 43.95%.The emission of construction machinery in Chengdu exhibited a clear monthly trend,with the highest from April to October and the lowest from November to March.In addition,the exhaust emissions presented an obvious spot-like characteristics,and the high-value areas were mainly concentrated in the surrounding suburban counties such as Shuangliu Wenjiang etc.To reduce pollution from construction machinery and improve the quality of the atmospheric environment,more effective measures on housing construction and municipal construction should be taken in those districts in Chengdu.

Progressively narrow the gap of PM_(2.5) pollution characteristics at urban and suburban sites in a megacity of Sichuan Basin, China

Nowadays,the fine particle pollution is still severe in some megacities of China,especially in the Sichuan Basin,southwestern China.In order to understand the causes,sources,and impacts of fine particles,we collected PM_(2.5)samples and analyzed their chemical composition in typical months from July 2018 to May 2019 at an urban and a suburban (background) site of Chengdu,a megacity in this region.The daily average concentrations of PM_(2.5)ranged from5.6-102.3μg/m^(3)and 4.3-110.4μg/m^(3)at each site.Secondary inorganics and organic matters were the major components in PM_(2.5)at both sites.The proportion of nitrate in PM_(2.5)has exceeded sulfate and become the primary inorganic component.SO_(2)was easier to transform into sulfate in urban areas because of Mn-catalytic heterogeneous reactions.In contrast,NO_(2)was easily converted in suburbs with high aerosol water content.Furthermore,organic carbon in urban was much greater than that in rural,other than elemental carbon.Element Cr and As were the key cancer risk drivers.The main sources of PM_(2.5)in urban and suburban areas were all secondary aerosols (42.9%,32.1%),combustion (16.0%,25.2%) and vehicle emission (15.2%,19.2%).From clean period to pollution period,the contributions from combustion and secondary aerosols increased markedly.In addition to tightening vehicle controls,urban areas need to restrict emissions from steel smelters,and suburbs need to minimize coal and biomass combustion in autumn and winter.

Effects of relative humidity and PM2.5 chemical compositions on visibility impairment in Chengdu, China

To better understand the potential causes of visibility impairment in autumn and winter in Chengdu,relative humidity(RH),visibility,the concentrations of PM2.5 and its chemical components were on-line measured continuously in Chengdu from Nov.2016 to Jan.2017.Six obvious haze episodes occurred in Chengdu,with the total time of haze episodes accounted for more than 90%of the total observation period,and higher NO2 concentrations and RH were related to the high particle concentrations in haze episodes.The visibility decreased in a non-linear tendency under different RH conditions with the increase of PM2.5 concentrations,which was more sensitive to RH under lower PM2.5 concentrations.The threshold concentration of PM2.5 got more smaller with the increase of RH.During the entire observation period,organic matter(OM)was the largest contributor(31.12%to extinction coefficient(bext)),followed by NH4NO3 and(NH4)2SO4 with 28.03%and 23.01%,respectively.However,with the visibility impairment from Type I(visibility>10 km)to Type IV(visibility≤2 km),the contribution of OM to bextdecreased from 38.12%to 26.77%,while the contribution of NH4NO3 and(NH4)2SO4 to bextincreased from 19.09%and 20.20%to 34.29%and 24.35%,respectively,and NH4NO3 became the largest contributor to bextat Type IV.The results showed that OM and NH4NO3 were the key components of PM2.5 for visibility impairment in Chengdu,indicating that the control of precursors emissions of carbonaceous species and NH4NO3 could effectively improve the visibility in Chengdu.

Biogenic volatile organic compound emission patterns and secondary pollutant formation potentials of dominant greening trees in Chengdu,southwest China

Integral to the urban ecosystem,greening trees provide many ecological benefits,but the active biogenic volatile organic compounds(BVOCs)they release contribute to the production of ozone and secondary organic aerosols,which harm ambient air quality.It is,therefore,necessary to understand the BVOC emission characteristics of dominant greening tree species and their relative contribution to secondary pollutants in various urban contexts.Consequently,this study utilized a dynamic enclosure system to collect BVOC samples of seven dominant greening tree species in urban Chengdu,Southwest China.Gas chromatography/mass spectrometry was used to analyze the BVOC components and standardized BVOC emission rates of each tree species were then calculated to assess their relative potential to form secondary pollutants.We found obvious differences in the composition of BVOCs emitted by each species.Ficus virens displayed a high isoprene emission rate at31.472μgC/(gdw(g dry weight)·hr),while Cinnamomum camphora emitted high volumes of D-Limonene at 93.574μgC/(gdw·hr).In terms of the BVOC emission rates by leaf area,C.camphora had the highest emission rate of total BVOCs at 13,782.59μgC/(m^(2)·hr),followed by Cedrus deodara with 5466.86μgC/(m^(2)·hr).Ginkgo biloba and Osmanthus fragrans mainly emitted oxygenated VOCs with lower overall emission rates.The high BVOC emitters like F.virens,C.camphora,and Magnolia grandiflora have high potential for significantly contributing to environmental secondary pollutants,so should be cautiously considered for future planting.This study provides important implications for improving urban greening efforts for subtropical Chinese urban contexts,like Chengdu.

Characteristics of ambient volatile organic compounds during spring O_(3) pollution episode in Chengdu,China

Surface ozone(O_(3))has become a critical pollutant impeding air quality improvement in many Chinese megacities.Chengdu is a megacity located in Sichuan Basin in southwest China,where O_(3)pollution occurs frequently in both spring and summer.In order to understand the elevated O_(3)during spring in Chengdu,we conducted sampling campaign at three sites during O_(3)pollution episodes in April.Volatile organic compounds(VOCs)compositions at each site were similar,and oxygenated VOCs(OVOCs)concentrations accounted for the highest proportion(35%-45%),followed by alkanes,alkens(including acetylene),halohydrocarbons,and aromatics.The sensitivity of O_(3)to its precursors was analyzed using an observation based box model.The relative incremental reactivity of OVOCs was larger than other precursors,suggesting that they also played the dominant role in O_(3)formation.Furthermore,the positive matrix factorization model was used to identify the dominant emission sources and to evaluate their contribution to VOCs in the city.The main sources of VOCs in spring were from combustion(27.75%),industrial manufacturing(24.17%),vehicle exhaust(20.35%),and solvent utilization(18.35%).Discussions on VOCs and NO_(x)reduction schemes suggested that Chengdu was typical in the VOC-limited regime,and VOC emission reduction would help to prevent and control O_(3).The analysis of emission reduction scenarios based on VOCs sources showed that the emission reduction ratio of VOCs to NO_(2)needs to reach more than 3 in order to achieve O_(3)prevention.Emission reduction from vehicular exhaust source and solvent utilization source may be more effective.