Oxygen vacancy （Ov） has significant influence on physical and chemical properties of TiO2 systems, especially on surface catalytic processes. In this work, we investigate the effects of Ov on the adsorption of forma...Oxygen vacancy （Ov） has significant influence on physical and chemical properties of TiO2 systems, especially on surface catalytic processes. In this work, we investigate the effects of Ov on the adsorption of formaldehyde （HCHO） on TiO2（110） surfaces through first- principles calculations. With the existence of Ov, we find the spatial distribution of surface excess charge can change the relative stability of various adsorption configurations. In this case, the bidentate adsorption at five-coordinated Ti （Tisc） can be less stable than the monodentate adsorption. And HCHO adsorbed in Ov becomes the most stable structure. These results are in good agreement with experimental observations, which reconcile the long-standing deviation between the theoretical prediction and experimental results. This work brings insights into how the excess charge affects the molecule adsorption on metal oxide surface.展开更多
Density functional theory（DFT）based ab-initio calculations were used to study formaldehyde（CH_2O）adsorptive behavior on graphene sheet.The results indicate that formaldehyde molecule is weakly bound to graphene wi...Density functional theory（DFT）based ab-initio calculations were used to study formaldehyde（CH_2O）adsorptive behavior on graphene sheet.The results indicate that formaldehyde molecule is weakly bound to graphene with small adsorption values（approximately-0.064eV）,but the interaction between CH_2O and graphene sheets can be greatly strengthened by means of doped atoms,which can provide a basis for the development of CH_2O storage materials.展开更多
Catalytic elimination of formaldehyde(HCHO) was investigated over Cu-Al_2O_3 catalyst at room temperature. The results indicated that no oxidation of HCHO into CO_2 occurs at room temperature, but the adsorption of H...Catalytic elimination of formaldehyde(HCHO) was investigated over Cu-Al_2O_3 catalyst at room temperature. The results indicated that no oxidation of HCHO into CO_2 occurs at room temperature, but the adsorption of HCHO occurs on the catalyst surface. With the increase of gas hourly space velocity(GHSV) and inlet HCHO concentration, the time to reach saturation was shortened proportionally. The results of the in situ DRIFTS, Density functional theory calculations and temperature programmed desorption(TPD) showed that HCHO was completely oxidized into HCOOH over Cu-Al_2O_3 at room temperature. With increasing the temperature in a flow of helium, HCOOH was completely decomposed into CO_2 over the catalyst surface, and the deactivated Cu-Al_2O_3 is regenerated at the same time. In addition, although Cu had no obvious influence on the adsorption of HCHO on Al_2O_3, Cu dramatically lowered the decomposition temperature of HCOOH into CO_2. It was shown that Cu-Al_2O_3 catalyst had a good ability for the removal of HCHO, and appeared to be promising for its application in destroying HCHO at room temperature.展开更多
The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount...The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.展开更多
A novel nano-TiO2-xNx composite was used as photocatalyst and added to the interior wall paint. The average diameter of nano-TiO2-xNx was about 20 nm. The majority crystal component of the sample was anatase and its o...A novel nano-TiO2-xNx composite was used as photocatalyst and added to the interior wall paint. The average diameter of nano-TiO2-xNx was about 20 nm. The majority crystal component of the sample was anatase and its optical absorption edge was shifted from 387 nm to 520 nm significantly. Nano-composite paint containing different dosage of nano- TiO2-xNx was investigated to study the properties of formaldehyde decomposition in the air. Testing results show that the formaldehyde decomposition ratio of that nano-paint can almost reach above 80%, especially for that of the paint containing 3% （w/w） nano-TiO2-xNx which exceeded 90%. The primary investigation on the reaction kinetics of photocatalytic formaldehyde decomposition indicated that the experiment data well fit the model of first-order reaction kinetics.展开更多
Powder quartz(PQ)/nano-TiO2composite was prepared by a mechanochemical method. Based on as-prepared PQ/nano-TiO2composite, we prepared interior paints and investigated the degradation efficiency of formaldehyde(DEF). ...Powder quartz(PQ)/nano-TiO2composite was prepared by a mechanochemical method. Based on as-prepared PQ/nano-TiO2composite, we prepared interior paints and investigated the degradation efficiency of formaldehyde(DEF). Scanning electron microscopy showed that nano-TiO2got well dispersed by the adding of PQ. Thermogravimetric analysis indicated that the mass ratio of 4:1 was a relatively good proportion for the most production of PQ/nano-TiO2composite. Fourier transform-infrared spectrometry showed that the peak position of Ti-O-Si bond varied with the milling time. At the early stage, no characteristic peak of Ti-O-Si bond was observed, while at the later stage, new peaks at 902 cm-1and 937 cm-1appeared. Meanwhile, PQ/nano-TiO2composite-based interior paint exhibited significant DEF of 96.3% compared to that consisting of sole nanoTiO2of 92.0% under visible light illumination. As an abundant mineral resource, PQ would make interior paints with HCHO purifying effect much more efficient and cheaper.展开更多
Porous carbon spheres are prepared by direct carbonization of potassium salt of resorcinol-formaldehyde resin spheres, and are investigated as COadsorbents. It is found that the prepared carbon materials still maintai...Porous carbon spheres are prepared by direct carbonization of potassium salt of resorcinol-formaldehyde resin spheres, and are investigated as COadsorbents. It is found that the prepared carbon materials still maintain the typical spherical shapes after the activation, and have highly developed ultra-microporosity with uniform pore size, indicating that almost the activation takes place in the interior of the polymer spheres. The narrow-distributed ultra-micropores are attributed to the "in-situ homogeneous activation"effect produced by the mono-dispersed potassium ions as a form of -OK groups in the bulk of polymer spheres. The CS-1 sample prepared under a KOH/resins weight ratio of 1 shows a very high COcapture capacity of 4.83 mmol/g and good CO/Nselectivity of7-45. We believe that the presence of a welldeveloped ultra-microporosity is responsible for excellent COsorption performance at room temperature and ambient pressure.展开更多
基金This work was supported by a grant from the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)of the Korean government(2021R1A3B1068304).The authors also acknowledge the support provided by a grant from the NRF funded by MSIT of the Korean government(RS-2023-00243840)and Brain Pool program(RS-2023-00222393).D.W.Boukhvalov acknowledges support from Jiangsu Innovative and Entrepreneurial Talents Project,and the Ministry of Science and Education of Russian Federation(FEUZ-2023-0013).
文摘通过氮掺杂TiO_(2)(N-TiO_(2))浸渍蜂窝过滤器构建了一系列原型光催化空气净化器(AP(N_(x)-C_(y)))系统,并用于在UV-LED光(1 W)照射条件下光催化分解0.5-5 ppm甲醛(CH_(2)O)蒸汽.在上述催化过滤器系统中,Nx和Cy分别代表N/Ti摩尔比(0-20)和N-TiO_(2)浓度(2-20 mg mL^(-1)).光催化分解实验结果表明,AP(N_(10)-C_(10))的性能最好,其催化CH2O转化为CO_(2)的转化率最高,循环反应10次后CO_(2)产率仍达到89.2%,在干燥空气中的清洁空气输送速率为9.45 L min^(-1).N10-C10的电荷载流子寿命(τa:1.70 ns)优于其他样品(如纯TiO_(2)的电荷载流子寿命为1.37 ns),这表明N缺陷(No)有助于降低带隙(3.10 eV)和产生氧空位OVs-Ti^(3+),这与密度泛函理论(DFT)模拟结果一致.采用原位漫反射红外傅里叶变换、电子顺磁共振和DFT分析等多种方法研究了CH_(2)O的光催化氧化途径.结果表明,氧化过程涉及多个能量有利的中间步骤(例如CH2O以CH_(2)O_(2)的形式在TiO_(2)-OV{110}表面的桥连O/OH基团上发生放热共价吸附,随后通过催化脱氢/氧化反应直接生成CO_(2):CH_(2)O_(2)/HCOO^(-)+•OH→H_(2)O+CO_(2)).这些步骤与具有N杂质的{101}表面上化学活性Ti原子的态密度计算结果一致.预计No缺陷和OVs的存在将通过降低活化能垒来影响反应能量和中间产物,从而在加湿条件下实现有效的矿化.综上,本文为设计和构建先进的光催化系统,并用于环境空气中醛类挥发性有机物(VOCs)的有效矿化提供了新思路.
文摘Oxygen vacancy （Ov） has significant influence on physical and chemical properties of TiO2 systems, especially on surface catalytic processes. In this work, we investigate the effects of Ov on the adsorption of formaldehyde （HCHO） on TiO2（110） surfaces through first- principles calculations. With the existence of Ov, we find the spatial distribution of surface excess charge can change the relative stability of various adsorption configurations. In this case, the bidentate adsorption at five-coordinated Ti （Tisc） can be less stable than the monodentate adsorption. And HCHO adsorbed in Ov becomes the most stable structure. These results are in good agreement with experimental observations, which reconcile the long-standing deviation between the theoretical prediction and experimental results. This work brings insights into how the excess charge affects the molecule adsorption on metal oxide surface.
基金National Natural Science Foundation of China(No.51201155)Natural Science Foundation of Shanxi Province(No.2012011019-1,2012011007-1)
文摘Density functional theory（DFT）based ab-initio calculations were used to study formaldehyde（CH_2O）adsorptive behavior on graphene sheet.The results indicate that formaldehyde molecule is weakly bound to graphene with small adsorption values（approximately-0.064eV）,but the interaction between CH_2O and graphene sheets can be greatly strengthened by means of doped atoms,which can provide a basis for the development of CH_2O storage materials.
基金The National Natural Science Foundation of China(No. 40275038)
文摘Catalytic elimination of formaldehyde(HCHO) was investigated over Cu-Al_2O_3 catalyst at room temperature. The results indicated that no oxidation of HCHO into CO_2 occurs at room temperature, but the adsorption of HCHO occurs on the catalyst surface. With the increase of gas hourly space velocity(GHSV) and inlet HCHO concentration, the time to reach saturation was shortened proportionally. The results of the in situ DRIFTS, Density functional theory calculations and temperature programmed desorption(TPD) showed that HCHO was completely oxidized into HCOOH over Cu-Al_2O_3 at room temperature. With increasing the temperature in a flow of helium, HCOOH was completely decomposed into CO_2 over the catalyst surface, and the deactivated Cu-Al_2O_3 is regenerated at the same time. In addition, although Cu had no obvious influence on the adsorption of HCHO on Al_2O_3, Cu dramatically lowered the decomposition temperature of HCOOH into CO_2. It was shown that Cu-Al_2O_3 catalyst had a good ability for the removal of HCHO, and appeared to be promising for its application in destroying HCHO at room temperature.
基金Project supported by the Science Project of Harbin City(No. H2001-12)the Youth Foundation of School of Municipal and Environmental Engineering in Harbin Institute of Technology(No. 01306914).
文摘The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.
基金Project supported by the Foundation of National Key Technologies R&D Program--Shanghai World Expo Special Project (Grant No.04DZ05803)
文摘A novel nano-TiO2-xNx composite was used as photocatalyst and added to the interior wall paint. The average diameter of nano-TiO2-xNx was about 20 nm. The majority crystal component of the sample was anatase and its optical absorption edge was shifted from 387 nm to 520 nm significantly. Nano-composite paint containing different dosage of nano- TiO2-xNx was investigated to study the properties of formaldehyde decomposition in the air. Testing results show that the formaldehyde decomposition ratio of that nano-paint can almost reach above 80%, especially for that of the paint containing 3% （w/w） nano-TiO2-xNx which exceeded 90%. The primary investigation on the reaction kinetics of photocatalytic formaldehyde decomposition indicated that the experiment data well fit the model of first-order reaction kinetics.
基金Funded by the National Natural Science Foundation of China(No.41130746)
文摘Powder quartz(PQ)/nano-TiO2composite was prepared by a mechanochemical method. Based on as-prepared PQ/nano-TiO2composite, we prepared interior paints and investigated the degradation efficiency of formaldehyde(DEF). Scanning electron microscopy showed that nano-TiO2got well dispersed by the adding of PQ. Thermogravimetric analysis indicated that the mass ratio of 4:1 was a relatively good proportion for the most production of PQ/nano-TiO2composite. Fourier transform-infrared spectrometry showed that the peak position of Ti-O-Si bond varied with the milling time. At the early stage, no characteristic peak of Ti-O-Si bond was observed, while at the later stage, new peaks at 902 cm-1and 937 cm-1appeared. Meanwhile, PQ/nano-TiO2composite-based interior paint exhibited significant DEF of 96.3% compared to that consisting of sole nanoTiO2of 92.0% under visible light illumination. As an abundant mineral resource, PQ would make interior paints with HCHO purifying effect much more efficient and cheaper.
基金the financial supports by the Natural Science Foundation of China (NSFC21576158, 21476132, 21576159 and 21403130)Shandong Provincial Natural Science Foundation, China (No. 2015 ZRB01765)
文摘Porous carbon spheres are prepared by direct carbonization of potassium salt of resorcinol-formaldehyde resin spheres, and are investigated as COadsorbents. It is found that the prepared carbon materials still maintain the typical spherical shapes after the activation, and have highly developed ultra-microporosity with uniform pore size, indicating that almost the activation takes place in the interior of the polymer spheres. The narrow-distributed ultra-micropores are attributed to the "in-situ homogeneous activation"effect produced by the mono-dispersed potassium ions as a form of -OK groups in the bulk of polymer spheres. The CS-1 sample prepared under a KOH/resins weight ratio of 1 shows a very high COcapture capacity of 4.83 mmol/g and good CO/Nselectivity of7-45. We believe that the presence of a welldeveloped ultra-microporosity is responsible for excellent COsorption performance at room temperature and ambient pressure.
