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.

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.

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.

A kinetic study of the reaction of ozone with ethylene in a smog chamber under atmospheric conditions

Ozone is one of the key species in the processes of atmospheric chemistry, which can be taken as an indicator of oxidation capacity in the troposphere. The reaction of ozone with reactive gases is an important process in the troposphere. Experimental simulation equipment of smog chamber for atmospheric reactions is used to study the reaction of ozone with ethylene in real atmospheric environment with ozone concentrations of 100―200 ppb. The concentrations of ozone and ethylene were moni-tored during the reaction with the combination of Model 49C-O_3 Analyzer and GC-FID. A rate constant of 1.01×10^(-18) (cm^3·mol^(-1)·s-(~1)) was obtained at 286.5 K, under condition of which the half-life of ozone was 88 min. The results obtained from our experiments are in excellent agreement with those reported previously by other researchers under extremely low pressure in terms of matrixisolation technology. This demonstrates that our equipment of smog chamber for atmospheric reactions is reliable, which can be used for further research of the processes of atmospheric reactions.

Smog chamber studies of ozone formation potentials for isopentane

The incremental reactivity and ozone formation potential of isopentane have been studied with chamber experiments and computer simulations. The chemical mechanism used in the computer simulations is an isopentane sub-mechanism from the Master Chemical Mechanism (MCM). The results from the chamber experiments suggest that the MCM can well simulate i-C5H12-NOx chamber experiments. The heterogeneous reaction of NO2 and water is an important source for OH radicals in the chamber experiments. The photolysis of HONO is responsible for the initiation of isopentane in photochemical reactions. The reaction rate constant for NO2 → HONO was determined to be 3.9×10-4―5.9×10-3 min-1 by conducting 3 sets of CO-NOx-air irradiations. 5 sets of isopentane-NOx irradiations under different conditions were performed in our chamber. Compared with the experiment with a low relative humidity (RH), an increase in RH can increase the reaction rate of NO2 with H2O, so that the peak ozone occurs earlier. When isopentane is predominant over NOx, the peak ozone concentration is largely dependent on NOx concentrations.

Effects of different introduction methods of Ce^4+and Zr^4+on denitration performance and anti-K poisoning performance of V2O5-WO3/TiO2 catalyst

The purpose of this work is to explore the effects of the introduction methods of Ce^4+and Zr^4+on the physicochemical properties,activity,and K tolerance of V2 O5-WO3/TiO2 catalyst for the selective catalytic reduction of NOx by NH3.Four different methods,namely pre-impregnation,post-impregnation,coimpregnation,and co-precipitation,were used to synthesize a series of V2 O5-WO3-TiO2-CeO2-ZrO2 catalysts.The catalysts were characterized by XRD,BET,NH3-TPD,XPS,and H2-TPR techniques.Moreover,the activity and anti-K poisoning performance were tested by an NH3-SCR model reaction.The results show that the introduction of Ce^4+and Zr^4+can improve the catalytic performance of V2O5-WO3/TiO2 catalyst,but the impregnation method cannot enhance the anti-K poisoning performance.Ce^4+and Zr^4+introduced by co-precipitation method can effectively improve the tolerance of K,which is mainly due to the incorporation of Ce^4+and Zr^4+into TiO2 lattice to form a uniform TiO2-CeO2-ZrO2 solid solution,resulting in the optimal surface acidity and redox performance,and reducing the decreases caused by Kpoisoning.Furthermore,based on the best introduction method,we further optimized the molar ratio of Ce^4+/Zr^4+,It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce^4+/Zr^4+is 2:1.

Doping effect of rare earth metal ions Sm^(3+),Nd^(3+)and Ce^(4+)on denitration performance of MnO_(x) catalyst in low temperature NH_(3)-SCR reaction

The MnXO_(x) catalysts(i.e.,MnSmO_(x),MnNdO_(x),MnCeO_(x)) were prepared by reverse co-precipitation method and used for NH_(3)-SCR reaction.It is found that MnCeO_(x) catalyst presents the best low tempe rature catalytic activity(higher than 90% NO_(x) conversion in the te mperature range from 125 to 225℃)and excellent H_(2)O+SO_(2) resistance.In order to explore the reason for this result,the characterization of X-ray diffraction(XRD),Raman spectroscopy,Brunauer-Emmett-Teller(BET),H_(2)-temperature programmed reduction(H_(2)-TPR),NH_(3)-temperature programmed desorption(NH_(3)-TPD),X-ray photoelectron spectroscopy(XPS) and in situ diffuse reflaxions infrared Fourier transformations spectroscopy(DRIFTS) were conducted.The obtained results suggest that MnCeO_(x) catalyst shows the largest amount of acid sites and the best reducibility among these MnXO_(x) catalysts.Besides,Ce^(4+) doping inhibits the crystallization of MnO_(x) catalyst and shows the largest specific surface area.Finally,in situ DRIFTS experiments reveal that NH_(3)-SCR reaction over MnCeO_(x) catalyst follows both Langmuir-Hinshelwood(LH) and Eley-Rideal(E-R) mechanisms,which is through "fast SCR" reaction.

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.