Enhanced Cr(vi) immobilization on goethite derived from an extremely acidic environment
作者：
Wang, Xiaobing;Chen, Na;Zhang, Lizhi*
期刊：
Environmental Science: Nano ,2019年6(7):2185-2194 ISSN：2051-8153
通讯作者：
Zhang, Lizhi
作者机构：
[Zhang, Lizhi; Wang, Xiaobing; Chen, Na] Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Minist Educ, Inst Environm & Appl Chem, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Zhang, Lizhi] C;Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Minist Educ, Inst Environm & Appl Chem, Wuhan 430079, Hubei, Peoples R China.
摘要：
Iron (hydr)oxides play an indispensable role in the immobilization of heavy metal ions in environmental geochemical processes. As is well-known, the mineralization process of iron (hydr)oxides strongly depends on their surrounding environment. Goethite, a common iron oxide hydrate, is often naturally mineralized or artificially prepared in an alkaline environment; therefore, most of the studies are limited to alkaline environment-derived goethite; moreover, although the mineralization of goethite often takes place in an extremely acidic environment (e.g., acid mine drainage), little information is available on the heavy metal ion immobilization ability of acidic environment-derived goethite. In this study, we investigated the mineralization of goethite in an extremely acidic environment (GA) and compared its Cr(vi) immobilization performance with that of the alkaline-derived counterpart (GB). It was interestingly found that the maximum amount and apparent rate of Cr(vi) immobilization for GA were 0.124 mg m-2 and 15.68 m-2 mg-1 min-1, 2.4 times and 2.9 times those of GB, respectively. This outstanding Cr(vi) immobilization performance of GA was attributed to its higher surface hydroxyl concentration, as evidenced by the in situ IR spectra and X-ray photoelectron spectra. The higher surface hydroxyl concentration of GA originated from the preferential growth of its {021} facet with higher -OH group density in an acidic environment, resulting in its higher facet proportion of {021}/{110}. Moreover, we carefully identified the coordination mode of Cr(vi) immobilized on the GA and GB surface using Cr K-edge near-edge structure spectroscopy and discovered the formation of both monodentate mononuclear and bidentate binuclear complexes. These findings shed light on the influence of acidity on the mineralization and heavy metal pollutant adsorption performance of goethite and also provide a method for the preparation of goethite with high heavy metal ion immobilization performance. © 2019 The Royal Society of Chemistry.
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英文
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Fast transformation of roxarsone into toxic arsenic species with ferrous iron and tetrapolyphosphate
作者：
Chen, Na;Wan, Yichao;Ai, Zhihui;Jia, Falong* ;Zhang, Lizhi
期刊：
Environmental Chemistry Letters ,2019年17(2):1077-1084 ISSN：1610-3653
通讯作者：
Jia, Falong
作者机构：
[Zhang, Lizhi; Chen, Na; Ai, Zhihui; Jia, Falong; Wan, Yichao] Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Inst Environm Chem, Minist Educ,Coll Chem, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Jia, Falong] C;Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Inst Environm Chem, Minist Educ,Coll Chem, Wuhan 430079, Hubei, Peoples R China.
关键词：
Roxarsone;Transformation;Molecule oxygen activation;Ferrous-tetrapolyphosphate complex
摘要：
Organoarsenic compounds have been widely used as feed additives in livestock and poultry breeding. They are excreted in manure and thus cause environmental pollution. Moreover, organoarsenic compounds can be transformed into other arsenic species with higher toxicity. There is little knowledge on the transformation of organoarsenic compounds in the presence of iron species. Here, we studied the transformation of roxarsone (4-hydroxy-3-nitrophenylarsonic acid) in the presence of ferrous ion (Fe(II)) and tetrapolyphosphate. Various generated arsenic species were monitored. Results show that 94.8% of roxarsone was degraded within 30min in 10mmolL(-1) Fe(II) and 50mmolL(-1) tetrapolyphosphate under air atmosphere. 70%of roxarsone arsenic was converted to As(V) species by hydroxyl radicals generated in the air system. Moreover, roxarsone is reductively transformed into other organoarsenic compounds, for example 4-hydroxy-3-aminophenylarsonic acid, by accepting electrons from the Fe(II)-tetrapolyphosphate complex. The toxicity and mobility of the generated inorganic or organic arsenic species are higher than those of roxarsone, which may induce serious environment and human health problems.
语种：
英文
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Dechlorination-Hydroxylation of Atrazine to Hydroxyatrazine with Thiosulfate: A Detoxification Strategy in Seconds
作者：
Mu, Yi;Zhan, Guangming;Huang, Cuimei;Wang, Xiaobing;Ai, Zhihui* ;...
期刊：
Environmental Science & Technology ,2019年53(6):3208-3216 ISSN：0013-936X
通讯作者：
Ai, Zhihui;Zhang, Lizhi;Zou, Jianping
作者机构：
[Huang, Cuimei; Zhang, Lizhi; Mu, Yi; Wang, Xiaobing; Ai, ZH; Zhang, LZ; Zhan, Guangming; Ai, Zhihui] Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Minist Educ, Inst Environm Chem, Wuhan 430079, Hubei, Peoples R China.;[Zou, Jianping; Mu, Yi; Luo, Shenglian] Nanchang Hangkong Univ, Key Lab Jiangxi Prov Persistent Pollutants Contro, Nanchang 330063, Jiangxi, Peoples R China.
通讯机构：
[Ai, ZH; Zhang, LZ] C;[Zou, Jianping] N;Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Minist Educ, Inst Environm Chem, Wuhan 430079, Hubei, Peoples R China.;Nanchang Hangkong Univ, Key Lab Jiangxi Prov Persistent Pollutants Contro, Nanchang 330063, Jiangxi, Peoples R China.
摘要：
Hydroxylation of atrazine to nontoxic hydroxyatrazine is generally considered an efficient detoxification method to remediate atrazine-contaminated soil and water. However, previous studies suggested that hydroxylation was not the dominant pathway for atrazine degradation in the hydroxyl radical-generating systems such as Fenton reaction, ozonation and UV/H2O2. Herein we report that the addition of sodium thiosulfate can realize rapid hydroxylation of atrazine to hydroxyatrazine at pH ≤ 4 under room temperature. High resolution mass spectra and isotope experiments results revealed that the hydroxylation of atrazine was involved with nucleophilic substitution and subsequent hydrolysis reaction as follows. HS2O3-, as a species of thiosulfate only at pH ≤ 4, first attacked C atom connecting to chlorine of atrazine to dechlorinate atrazine and produce C8H14N5S2O3-. Subsequently, the S-S bond of C8H14N5S2O3- was cleaved easily to form SO3 and C8H14N5S-. Next, C8H14N5S- was hydrolyzed to generate hydroxyatrazine and H2S. Finally, the comproportionation of SO3 and H2S in situ produced S0 during hydroxylation of atrazine with thiosulfate. This study clarifies the importance of degradation pathway on the removal of pollutants, and also provides a nonoxidative strategy for atrazine detoxification in seconds. Copyright © 2019 American Chemical Society.
语种：
英文
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Photochemical behavior of ferrihydrite-oxalate system: Interfacial reaction mechanism and charge transfer process
作者：
Xu, Tianyuan;Zhu, Runliang;Shang, Huan;Xia, Yabei;Liu, Xiao* ;...
期刊：
Water Research ,2019年159:10-19 ISSN：0043-1354
通讯作者：
Liu, Xiao
作者机构：
[Zhang, Lizhi; Shang, Huan; Xia, Yabei; Liu, Xiao; Xu, Tianyuan] Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Inst Environm & Appl Chem, Minist Educ,Coll Chem, Wuhan 430079, Hubei, Peoples R China.;[Zhu, Runliang] Chinese Acad Sci, Guangdong Prov Key Lab Mineral Phys & Mat, Guangzhou Inst Geochem, 511 Kehua St, Guangzhou 510640, Guangdong, Peoples R China.
通讯机构：
[Liu, Xiao] C;Cent China Normal Univ, Key Lab Pesticide & Chem Biol, Inst Environm & Appl Chem, Minist Educ,Coll Chem, Wuhan 430079, Hubei, Peoples R China.
关键词：
Fe(III)-Ox complex;Ferrihydrite;In-situ ATR-FTIR;Oxalic acid;Reactive oxygen species
摘要：
Heterogeneous photochemical reactions associated with natural iron (hydr)oxides and oxalic acid have attracted a great deal of scientific attention in the application of organic pollutants degradation. However, the reaction mechanism is still unclear due to the complicated iron cycles and reactive oxygen species (ROS)generation. In this study, the in situ attenuated total reflectance-Fourier transform infrared spectroscopy was implemented to investigate the adsorption process and photochemical behavior of oxalic acid on the surface of ferrihydrite. A comprehensive reaction mechanism from the perspective of charge transfer process, including homogeneous-heterogeneous iron cycling and ROS generation, was illustrated in detail. We found that oxalic acid was first adsorbed on the surface of ferrihydrite with a mononuclear bidentate binding geometry. Interestingly, this mononuclear bidentate complex on the surface of ferrihydrite was stable under visible light irradiation. Subsequently, the whole complex departed from ferrihydrite surface through non-reduction dissolution with the form of Fe(C2O4)+. In the solution, the Fe(C2O4)+ complexes would quickly convert to Fe(C2O4)2− complexes. Under visible light irradiation, the electrons generated from the photolysis of Fe(C2O4)2− complex reacted with O2 to form O2•−/•OOH. Meanwhile, Fe(III)was reduced to Fe(II). Finally, the produced O2•−/•OOH could react with Fe(II)through a one-step way to generate •OH, which possessed higher •OH formation efficiency than that through the two-step way of H2O2 as the intermediates. This study helps us with understanding of in-situ photochemical reaction mechanism of ferrihydrite-oxalic acid system, and also provides guidance to effectively utilize widespread iron (hydr)oxides and organic acids in natural environment to develop engineered systems for water treatment. © 2019 Elsevier Ltd
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英文
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基于表面氧空位的光催化固氮材料
作者：
毛成梁;张礼知
期刊：
中国材料进展 ,2019年38(2):83-90 ISSN：1674-3962
通讯作者：
Zhang, L.
作者机构：
华中师范大学化学学院 环境与应用化学研究所 农药与化学生物学教育部重点实验室,湖北武汉,430079;[毛成梁; 张礼知] 华中师范大学
通讯机构：
Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan, China
关键词：
光催化;固氮;氧空位;卤氧铋;氢化氧化钛
摘要：
合成氨是基本的化工过程,对地球能源、环境和生命过程至关重要。Harbor-Bosch过程利用Fe催化剂开创性地实现了氮气还原固定为氨。由于氮气N≡≡N三键化学性质稳定,该反应需要在高温高压条件才能实现有效氮气固定。近年来,太阳能驱动的光催化固氮以其绿色温和的反应条件受到了广泛关注。最近,作者团队以卤氧铋和钌(Ru)/氢化氧化钛为模型催化剂,提出氧空位电子可有效活化氮气,即氧空位对氮气的直接电子传递或者氧空位电子经由Ru纳米晶传递给吸附态分子氮能有效弱化氮气N≡≡N三键,结合高效太阳光全光谱吸收材料,将光催化合成氨效率提高至接近传统热催化效率,为高效太阳光驱动固氮提供了新途径。从氧空位活性位点的构建出发,总结概括了含缺陷(尤其是氧空位)材料在光催化固氮的前沿进展,归纳了氧空位、氧空位和传统过渡金属中心耦合对氮气活化的机理。最后,基于对以上机理的理解,总结展望了光催化固氮面临的机遇与挑战,提出了可行的新型高效光催化固氮材料设计思路。
语种：
中文
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Oxygen vacancy promoted o2 activation over perovskite oxide for low-temperature co oxidation
作者：
Yang, Ji;Hu, Siyu;Fang, Yarong;Hoang, Son;Li, Li;...
期刊：
ACS CATALYSIS ,2019年9(11):9751-9763 ISSN：2155-5435
通讯作者：
Guo, Yanbing
作者机构：
[Zhang, Lizhi; Li, Li; Wu, Jian; Yang, Weiwei; Guo, Yanbing; Yang, Ji; Liang, Zhenfeng; Hu, Jinpeng; Luo, Zhu; Hoang, Son; Hu, Siyu; Pan, Chuanqi; Fang, Yarong] Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.;[Ding, Jun; Xiao, Wen] Natl Univ Singapore, Dept Mat Sci & Engn, Singapore 117576, Singapore.
通讯机构：
[Guo, Yanbing] C;Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
关键词：
monolithic catalyst;oxygen vacancy;surface oxygen activation;monatomic oxygen ion;perovskites
摘要：
The insights on the primary active oxygen specie and its relation with oxygen vacancy is essential for the design of low-temperature oxidation catalysts. Herein, oxygen vacancy-rich La0.8Sr0.2CoO3 with an ordered macroporous structure was integrated on the commercial ceramic monolith in large scale without additional adhesives via a facile in situ solution assembly. The constructed macropores not only contributed to the oxygen vacancy generation in catalyst preparation but also facilitated favorable mass transport during catalytic process. Combined with theoretical investigations and EPR, O2-TPD, H2-TPR observations, we revealed that monatomic oxygen ions (O-) are the primary oxygen active specie for perovskite oxide. And molecular O2 is more favorably adsorbed and activated on surface oxygen vacancies via a one electron transfer process to form monatomic oxygen ions (O-), thus boosting richness of active O- and the low-temperature oxidation of CO. Different with the preferential Eley-Rideal (E-R) mechanism on pristine LSCO surface, Langmuir-Hinshelwood (L-H) mechanism, in which O- reacts with adsorbed CO to finish the oxidation reaction, was more favorable on the oxygen vacancy rich surface. Our work here elucidates the primary active oxygen specie as well as its origin over perovskite oxides and paves a feasible pathway for rational design of high-performance catalysts in heterogeneous reactions. Copyright © 2019 American Chemical Society.
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英文
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Beyond the Thermal Equilibrium Limit of Ammonia Synthesis with Dual Temperature Zone Catalyst Powered by Solar Light
作者：
Mao, Chengliang;Li, Hao;Gu, Honggang;Wang, Jiaxian;Zou, Yunjie;...
期刊：
Chem ,2019年5(10):2702-2717 ISSN：2451-9294
通讯作者：
Zhang, Lizhi
作者机构：
[Zhang, Lizhi; Li, Hao; Shen, Wenjuan; Zou, Yunjie; Wang, Jiaxian; Mao, Chengliang; Zhao, Jincai; Li, Jie] Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.;[Gu, Honggang; Liu, Shiyuan] Huazhong Univ Sci & Technol, State Key Lab Digital Mfg Equipment & Technol, Wuhan 430074, Hubei, Peoples R China.;[Qi, Guodong; Xu, Jun; Deng, Feng] Chinese Acad Sci, State Key Lab Magnet Resonance & Atom & Mol Phys, CAS Key Lab Magnet Resonance Biol Syst, Wuhan Inst Phys & Math,Natl Ctr Magnet Resonance, Wuhan 430071, Hubei, Peoples R China.
通讯机构：
[Zhang, Lizhi] C;Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
关键词：
ammonia synthesis;black TiO2;equilibrium limit;Fe nanonecklace;nitrogen fixation;oxygen vacancy;photocatalysis;photothermal catalysis;plasmonic;SDG7: Affordable and clean energy;TiO2
摘要：
Plasmonic local heating effect of Fe nanonecklace endowed TiO2-xHy/Fe catalyst of hot-zone Fe and cool-zone TiO2-xHy, which were responsible for tandem N2 activation and NH3 assembly, respectively. With such dual temperature zones and the tandem kinetic mechanism, light-driven TiO2-xHy/Fe nanonecklace achieved highly efficient ammonia synthesis with NH3 yield beyond the thermodynamic equilibrium limit of thermocatalytic ammonia synthesis. © 2019 Elsevier Inc.Artificial ammonia synthesis (Haber-Bosch process) is a prototypical exothermic reaction of maximum catalytic yield restricted by the unbreakable equilibrium law. This is because bottlenecked N2 dissociation necessitates high temperature, but high temperature reversely shifts the thermal equilibrium toward NH3 decomposition. To surmount this equilibrium limit, here, we propose a new scenario of dual-temperature-zone catalysis. Powered by sunlight, the apparent temperature of TiO2-xHy/Fe hybrid reaches 495°C but with local temperature difference up to 137°C between the hot zone (Fe) and “cooling” zone (TiO2-xHy) owing to the plasmonic local heating effect. The hot Fe bearing hot carriers efficiently dissociates N2, while working-in-tandem TiO2-xHy well accommodates spilled-over N from Fe via successive hydrogenation, prominently mitigating the reverse equilibrium shift and thus delivering record NH3 concentrations of 1,939 (1 atm) and 19,620 ppm (10 atm) at 495°C, 1.55 and 1.57 times the theoretical equilibrium limits of 1,249 and 12,459 ppm, respectively. © 2019 Elsevier Inc.A key goal of contemporary ammonia synthesis is to reduce the consumption of fossil fuel by the design of more efficient thermocatalysts or “green” alternative pathways. However, the maximum NH3 yields of thermocatalysis are restricted by the thermodynamic equilibrium limit, while the catalytic efficiency of alternative pathway, like photocatalysis, is low in comparison with that of thermocatalysis. Here, we report an efficient solar light-driven N2 + 3H2 = 2NH3 via a photothermal pathway on a Fe-nanonecklace-hydrogenated titanium hybrid, generating NH3 with concentration beyond the equilibrium limit of thermocatalysis. The mechanism study reveals the reaction path of high-temperature N2 activation on Fe and low-temperature NH3 formation on TiO2-xHy, originating from the plasmonic local heating effect of Fe nanonecklace. This light-induced non-equilibrium catalysis ensures both high NH3 yield and high catalytic efficiency, and thus, it may be a promising alternative ammonia synthesis pathway. © 2019 Elsevier Inc.
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英文
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Hexavalent chromium removal by a new composite system of dissimilatory iron reduction bacteria Aeromonas hydrophila and nanoscale zero-valent iron
作者：
Shi, Zunji;Shen, Wenjuan;Yang, Kai;Zheng, Ningning;Jiang, Xiaofang;...
期刊：
Chemical Engineering Journal ,2019年362:63-70 ISSN：1385-8947
通讯作者：
Xie, Bo;Ai, Zhihui
作者机构：
[Xie, Bo; Yang, Dandan; Yang, Kai; Shi, Zunji; Jiang, Xiaofang; Zheng, Ningning; Liu, Limin] Cent China Normal Univ, Hubei Key Lab Genet Regulat & Integrat Biol, Sch Life Sci, Wuhan 430079, Hubei, Peoples R China.;[Zhang, Lizhi; Shen, Wenjuan; Ai, Zhihui] Cent China Normal Univ, Coll Chem, Minist Educ, Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.;[Shi, Zunji] Chinese Acad Sci, Key Lab Magnet Resonance Biol Syst, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan Ctr Magnet Resonance,Wuhan Inst Phys & Math, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Xie, Bo; Ai, Zhihui] C;Cent China Normal Univ, Hubei Key Lab Genet Regulat & Integrat Biol, Sch Life Sci, Wuhan 430079, Hubei, Peoples R China.;Cent China Normal Univ, Coll Chem, Minist Educ, Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.
关键词：
Aeromonas hydrophila;Anoxic reduction;Hexavalent chromium;Nanoscale zero-valent iron
摘要：
Core-shell Fe@Fe2O3 nanowire is one special nanoscale zero-valent iron (NZVI) with an iron core and an outside shell of iron oxide containing the surface bound ferrous ions, which has been used to remove various pollutants including Cr(VI). However, it can be easily oxidized to accumulate iron oxides on the shell, resulting in the loss of reactive activity during its long-term application. Therefore, the dissolution of iron oxides by reduction is required to maintain NZVI reactivity. In this study, we combine NZVI and a dissimilatory iron reduction bacteria (DIRB), Aeromonas hydrophila HS01, to establish a composite system for a sustainable anoxic reduction of Cr(VI). HS01 can stably coexist with NZVI, reduce the oxidized Fe on NZVI and generate more dissolved Fe(II) under anoxic conditions. This presence of HS01 can maintain the core-shell structured morphology and relatively more Fe0 and Fe(II) on NZVI surface, and enhance the reactivity in Cr(VI) removal. Our results indicated that a suitable DIRB can be used to prolong the reactivity of NZVI, and their combination is an efficient method for anoxic Cr(VI) removal. © 2019 Elsevier B.V.
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英文
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Molecular-scale structures of uranyl surface complexes on hematite facets
作者：
Huang, Xiaopeng;Hou, Xiaojing;Wang, Fan;Guo, Binghuang;Song, Fahui;...
期刊：
Environmental Science: Nano ,2019年6(3):892-903 ISSN：2051-8153
通讯作者：
Zhang, Lizhi;Ling, Lan
作者机构：
[Guo, Binghuang; Zhang, Lizhi; Hou, Xiaojing; Huang, Xiaopeng; Zhao, Jincai; Wang, Fan; Song, Fahui] Cent China Normal Univ, Inst Environm Chem, Coll Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.;[Ling, Lan] Tongji Univ, Coll Environm Sci & Technol, State Key Lab Pollut Control, Shanghai 200092, Peoples R China.
通讯机构：
[Zhang, Lizhi] C;[Ling, Lan] T;Cent China Normal Univ, Inst Environm Chem, Coll Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.;Tongji Univ, Coll Environm Sci & Technol, State Key Lab Pollut Control, Shanghai 200092, Peoples R China.
摘要：
As the fate, transport and bioavailability of U(vi) in subsurface environments are strongly influenced by its adsorption structures on iron minerals such as hematite, we systematically studied the molecular-scale structures of U(vi) complexes formed at the interfaces of hematite and water with periodic density-functional theory (DFT) calculation, extended X-ray absorption fine structure (EXAFS) measurements, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) integrated with X-ray energy dispersive spectroscopy (XEDS). The combined theoretical and experimental results revealed that U(vi) was complexed on three hematite facets in an inner-sphere coordination, but edge-sharing bidentate mononuclear (2E) complexes were formed on {001} facets, and corner-sharing bidentate binuclear (2C) ones were on both {012} and {110} facets. Moreover, the U(vi) adsorption site densities on the {012} and {110} facets of hematite were both about 0.32 #U nm-2, significantly higher than the adsorption site density (0.18 #U nm-2) on the {001} counterpart, which was consistent with the results of STEM-XEDS quantification. The results suggest that the U(vi) adsorption performance with hematite was strongly dependent on the coordination environment of U(vi) on the hematite facets. This study clarifies the molecular-scale structures of the U(vi) surface coordination on different hematite facets and also provides new insights into predicting the long-term fate and transport of highly radiotoxic actinyl ions in subsurface environments. © 2019 The Royal Society of Chemistry.
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英文
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Anion (O, N, C, and S) vacancies promoted photocatalytic nitrogen fixation
作者：
Mao, Chengliang;Wang, Jiaxian;Zou, Yunjie;Li, Hao;Zhan, Guangming;...
期刊：
Green Chemistry ,2019年21(11):2852-2867 ISSN：1463-9262
通讯作者：
Zhang, Lizhi
作者机构：
[Wang, Jiaxian; Zhang, Lizhi; Mao, Chengliang; Zhao, Jincai; Li, Hao; Li, Jie; Zhan, Guangming; Zou, Yunjie] Cent China Normal Univ, Inst Environm & Appl Chem, Coll Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Zhang, Lizhi] C;Cent China Normal Univ, Inst Environm & Appl Chem, Coll Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
摘要：
Mild-condition nitrogen fixation using "green" solar energy, merely requiring a solar-to-NH3 (STA) efficiency of 0.1% for potential use, is a promising alternative to the Haber-Bosch process but remains a great challenge. The bottleneck lies in the ultra-low efficiency originating from the sluggish surface reaction involving 6e-/6H+, specifically, the rate-limiting reductive activation of nitrogen. To meet this challenge, a common approach adopted by natural nitrogenase or artificial catalysts is to craft an active center (transition metal) of electron-rich nature, thus enriching the LUMO (lowest unoccupied molecular orbital) electron density of N2via the e- → π∗-orbital (N) transition to facilitate the molecular nitrogen activation. Recent progress suggests that anion vacancies such as O, C, N, and S vacancies, which inherently bear excess electrons and coordinatively unsaturated metal ions, could be explored in promoting the molecular nitrogen activation in photocatalysis. In this review, we summarize the in depth anion vacancy-dominated nitrogen photo-fixation systems, and then focus on the mechanical understanding of how an anion vacancy kinetically affects the nitrogen reductive activation including N-N triple bond weakening, N2 adsorption and activation energies, and kinetic pathways, and finally propose the future challenges and prospects of this emerging area. © 2019 The Royal Society of Chemistry.
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英文
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Interfacial Charging-Decharging Strategy for Efficient and Selective Aerobic NO Oxidation on Oxygen Vacancy
作者：
Li, Hao;Shang, Huan;Li, Yuhan;Cao, Xuemei;Yang, Zhiping;...
期刊：
Environmental Science & Technology ,2019年53(12):6964-6971 ISSN：0013-936X
通讯作者：
Ai, Zhihui;Zhang, Lizhi
作者机构：
[Zhang, Lizhi; Yang, Zhiping; Shang, Huan; Li, Hao; Ai, ZH; Zhang, LZ; Ai, Zhihui; Cao, Xuemei] Cent China Normal Univ, Inst Appl & Environm Chem, Minist Educ, Key Lab Pesticide & Chem Biol,Coll Chem, Wuhan 430079, Hubei, Peoples R China.;[Li, Yuhan] Chongqing Technol & Business Univ, Chongqing Key Lab Catalysis & New Environm Mat, Engn Res Ctr Waste Oil Recovery Technol & Equipme, Minist Educ,Coll Environm & Resources, Chongqing 400067, Peoples R China.
通讯机构：
[Ai, ZH; Zhang, LZ] C;Cent China Normal Univ, Inst Appl & Environm Chem, Minist Educ, Key Lab Pesticide & Chem Biol,Coll Chem, Wuhan 430079, Hubei, Peoples R China.
摘要：
Intelligent defect engineering to harness surface molecular processes is at the core of selective oxidation catalysis. Here, we demonstrate that the two-electron-trapped oxygen vacancy (VO) of BiOCl, a prototypical F center (VO′′), is a superb site to confine O2 toward efficient and selective NO oxidation to nitrate. Stimulated by solar light, VO′′ accomplishes NO oxidation through a two-electron charging (VO′′ + O2 → VO′′-O22-) and subsequent one-electron decharging process (VO′′-O22- + NO → VO-NO3- + e-). The back-donated electron is retrapped by VO to produce a new single-electron-trapped VO (VO′), simultaneously triggering a second round of NO oxidation (VO′-O2 + NO → VO-NO3-). This unprecedented interfacial charging-decharging scheme alters the peroxide-associated NO oxidation selectivity from NO2 to NO3- with a high efficiency and thus hold great promise for the treatment of risky NOx species in indoor air. © 2019 American Chemical Society.
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英文
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Liquid Nitrogen Activation of Zero-Valent Iron and Its Enhanced Cr(VI) Removal Performance
作者：
Hu, Yue;Peng, Xing;Ai, Zhihui;Jia, Falong* ;Zhang, Lizhi*
期刊：
Environmental Science & Technology ,2019年53(14):8333-8341 ISSN：0013-936X
通讯作者：
Jia, Falong;Zhang, Lizhi
作者机构：
[Zhang, Lizhi; Peng, Xing; Hu, Yue; Ai, Zhihui; Jia, Falong; Zhang, LZ] Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Jia, FL; Zhang, LZ] C;Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
摘要：
In this study, we report that liquid nitrogen treatment is a promising zero-valent iron activation method that does not remove the iron oxide shell; this can improve the apparent Cr(VI) removal rate constant of zero-valent iron by about 4-120 times, depending on the particle sizes and the suppliers of zero-valent iron. It was found that liquid nitrogen, with its low temperature of 77 K, could crack the iron oxide shell of zero-valent iron to produce abundant fractures because of the different thermal expansion coefficients of iron oxide and iron. These fractures provided suitable mass transfer channels for the inward transfer of water/oxygen molecules to the iron core and the subsequent in situ generation of Fe(II) for the reduction of Cr(VI) to Cr(III). More importantly, systematic characterizations confirmed the generation of an Fe(III)/Cr(III)/Cr(VI) composite on the surface of zero-valent iron during the removal, suggesting its environmental benignancy. This study provides a novel physical zero-valent iron activation method, sheds light on the importance of the iron oxide shell of zero-valent iron on Cr(VI) removal, and clarifies the intrinsic Cr(VI) removal mechanism of zero-valent iron. © 2019 American Chemical Society.
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Robust and well-controlled TiO2-Al2O3 binary nanoarray-integrated ceramic honeycomb for efficient propane combustion
作者：
Xiong, Juxia;Luo, Zhu;Yang, Ji;Guo, Yanbing* ;Piyadasa, Adimali;...
期刊：
CrystEngComm ,2019年21(17):2727-2735 ISSN：1466-8033
通讯作者：
Guo, Yanbing;Gao, Pu-Xian
作者机构：
[Zhang, Lizhi; Yang, Weiwei; Guo, Yanbing; Yang, Ji; Deng, Hongtao; Xiong, Juxia; Luo, Zhu; Hu, Siyu; Fang, Yarong] Cent China Normal Univ, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol, Minist Educ,Coll Chem, Wuhan 430079, Hubei, Peoples R China.;[Piyadasa, Adimali; Gao, Pu-Xian; Hoang, Son; Wang, Sibo] Univ Connecticut, Dept Mat Sci & Engn, Storrs, CT 06269 USA.;[Piyadasa, Adimali; Gao, Pu-Xian; Hoang, Son; Wang, Sibo] Univ Connecticut, Inst Mat Sci, Storrs, CT 06269 USA.
通讯机构：
[Guo, Yanbing] C;[Gao, Pu-Xian] U;Cent China Normal Univ, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol, Minist Educ,Coll Chem, Wuhan 430079, Hubei, Peoples R China.;Univ Connecticut, Dept Mat Sci & Engn, Storrs, CT 06269 USA.;Univ Connecticut, Inst Mat Sci, Storrs, CT 06269 USA.
摘要：
The catalytic total oxidation of short-chain alkanes released from automobile exhausts is still a big challenge in volatile organic compound (VOC) elimination. The significant degradation of catalytic activity after hydrothermal aging is a widely existing issue. Herein, we report a facile one-pot hydrothermal method to successfully grow TiO2-Al2O3 binary nanoarrays on the 3D channel surfaces of ceramic honeycombs. Such a binary nanoarray was heterogeneously integrated on the cordierite honeycomb channel surface with closely separated nanowire arrays of anatase-TiO2 and mesoporous γ-Al2O3, which exhibited excellent robustness under mechanical vibration and thermal and hydrothermal aging. Moreover, propane conversion with the Pt/TiO2-Al2O3 binary nanoarray catalyst rapidly reached 80% at a temperature as low as 224 °C, suggesting that the binary nanoarray catalyst is a promising candidate for practical applications. © 2019 The Royal Society of Chemistry.
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Oxygen Vacancies Promoted the Selective Photocatalytic Removal of NO with Blue TiO2 via Simultaneous Molecular Oxygen Activation and Photogenerated Hole Annihilation
作者：
Shang, Huan;Li, Meiqi;Li, Hao;Huang, Shun;Mao, Chengliang;...
期刊：
Environmental Science & Technology ,2019年53(11):6444-6453 ISSN：0013-936X
通讯作者：
Ai, Zhihui;Zhang, Lizhi
作者机构：
[Zhang, Lizhi; Shang, Huan; Mao, Chengliang; Li, Hao; Ai, ZH; Zhang, LZ; Huang, Shun; Ai, Zhihui; Li, Meiqi] Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Ai, ZH; Zhang, LZ] C;Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
摘要：
Semiconductor photocatalytic technology has great potential for the removal of dilute gaseous NO in indoor and outdoor atmospheres but suffers from unsatisfactory NO-removal selectivity due to undesirable NO2 byproduct generation. In this study, we demonstrate that the 99% selectivity of photocatalytic NO oxidation toward nitrate can be achieved over blue TiO2 bearing oxygen vacancies (OVs) under visible-light irradiation. First-principles density functional theory calculation and experimental results suggested that the OVs of blue TiO2 with localized electrons could facilitate the molecular oxygen activation through single-electron pathways to generate ·O2- and simultaneously promote the photogenerated hole annihilation. The generated ·O2- directly converted NO to nitrate, while the hole annihilation inhibited the side-reaction between holes and NO to avoid toxic NO2 byproduct formation, resulting in the highly selective removal of NO. This study reveals the dual functions of OVs in defective photocatalysts and also provides fundamental guidance for the selective purification of NO with photocatalytic technology. © 2019 American Chemical Society.
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英文
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Boosted photoelectrochemical immunosensing of metronidazole in tablet using coral-like g-C3N4 nanoarchitectures
作者：
Li, Xin;Yuan, Yijin;Pan, Xinmeng;Zhang, Lizhi;Gong, Jingming*
期刊：
Biosensors and Bioelectronics ,2019年123:7-13 ISSN：0956-5663
通讯作者：
Gong, Jingming
作者机构：
[Zhang, Lizhi; Gong, Jingming; Yuan, Yijin; Pan, Xinmeng; Li, Xin] Cent China Normal Univ, Coll Chem, Minist Educ, Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Gong, Jingming] C;Cent China Normal Univ, Coll Chem, Minist Educ, Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.
关键词：
Coral-like g-C(3)N(4);Metronidazole;Nanoarchitectured design;Oral medicine sample;Photoelectrochemical immunoassay
摘要：
A simple, facile and sensitive photoelectrochemical (PEC) bioassay protocol for metronidazole (MNZ) detection in common oral medicine samples has been proposed under visible-light irradiation, where novel hierarchical coral-like g-C 3 N 4 nanoarchitectures (cg-C 3 N 4 ) have been first explored as PEC sensing platform. Featured with the unique nanostructures (e.g., interlaced porous network architecture, and open boundaries), the as-formed cg-C 3 N 4 nanoarchitectures not only efficiently inhibit the recombination of photogenerated electron-hole but also enable the immobilization of capture antibodies as well as the antibody-antigen binding efficiency fluently, thus amplifying the photocurrent response. This newly constructed PEC immunoassay displays excellent performance for MNZ determination with high sensitivity and selectivity. Under the optimal condition, this bioassay protocol exhibits a linear range of 0.01–100 µM with a detection limit of 0.005 µM at signal to noise ratio of 3. The resulting PEC immunoassay has been proved to be applicable for sensing MNZ in common oral medicine samples. © 2018 Elsevier B.V.
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英文
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Visible light driven selective oxidation of amines to imines with BiOCl: Does oxygen vacancy concentration matter?
作者：
Mao, Chengliang;Cheng, Honggang;Tian, Hao;Li, Hao;Xiao, Wen-Jing;...
期刊：
Applied Catalysis B: Environmental ,2018年228:87-96 ISSN：0926-3373
通讯作者：
Zhang, Lizhi
作者机构：
[Zhang, Lizhi; Mao, Chengliang; Zhao, Jincai; Cheng, Honggang; Li, Hao; Xiao, Wen-Jing] Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Peoples R China.;[Xu, Hu; Tian, Hao] South Univ Sci & Technol China, Dept Phys, Shenzhen 518055, Peoples R China.
通讯机构：
[Zhang, Lizhi] C;Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Peoples R China.
关键词：
Bismuth oxychloride;Molecular oxygen activation;Oxygen vacancies;Photocatalysis;Selective amines oxidation
摘要：
The relationship between oxygen vacancy (OV) concentration of semiconductors and their photocatalytic performances is far from clarified. In this study, by tuning the OV concentration of BiOCl (001) surface via a novel H<inf>2</inf>O<inf>2</inf>treatment coupled infrared irradiation method, we demonstrate that OV concentration of BiOCl (001) surface strongly determine its surface atomic and electronic structures to modulate the photocatalytic pathways. Being of shorter Bi–Bi and Bi–O bond lengths as well as more electrons being less localized, BiOCl (001) surface with higher OV concentration favored molecular oxygen activation to generate O<inf>2</inf><sup>2−</sup>via a two-electron transfer pathway, while the generated O<inf>2</inf><sup>2−</sup>could prevent the over oxidation of amines and thus achieve high selectivity in the oxidation of amines to imines. Similar phenomena were also observed for other semiconductor photocatalysts such as TiO<inf>2</inf>and Nb<inf>2</inf>O<inf>5</inf>, suggesting the generality of oxygen vacancy concentration mediated selectivity enhancement. These findings shed light on the relationship between the oxygen vacancy concentration and the surface structure of semiconductor photocatalysts and offer a novel pathway to realize photocatalytic selective oxidation of amines to imines.<br/> ©2018 Elsevier B.V.
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英文
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Efficient light-driven CO2 hydrogenation on Ru/CeO2 catalysts
作者：
Quan, Fengjiao;Zhan, Guangming;Mao, Chengliang;Ai, Zhihui;Jia, Falong* ;...
期刊：
Catalysis Science & Technology ,2018年8(24):6503-6510 ISSN：2044-4753
通讯作者：
Jia, Falong
作者机构：
[Quan, Fengjiao; Zhang, Lizhi; Mao, Chengliang; Zhan, Guangming; Ai, Zhihui; Jia, Falong] Cent China Normal Univ, Coll Chem, Inst Environm Chem, Minist Educ,Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.;[Liu, Shiyuan; Gu, Honggang] Huazhong Univ Sci & Technol, State Key Lab Digital Mfg Equipment & Technol, Wuhan 430074, Hubei, Peoples R China.
通讯机构：
[Jia, Falong] C;Cent China Normal Univ, Coll Chem, Inst Environm Chem, Minist Educ,Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China.
摘要：
Light-driven heterogeneous catalysis provides a promising way to accomplish chemical reactions by the use of light energy, which reduces the consumption of chemical energy sources. Here, we show that Ru/CeO2 catalysts exhibit high activity for the hydrogenation of CO2 to methane under illumination only, reaching high CO2 conversion (over 99.9%) and selectivity of methane (∼100%) at low temperature. In sharp contrast, less CO2 is converted at the same temperature when a traditional heating model is used. As revealed by the results, the enhanced conversion rate under illumination should not only be attributed to the light-induced thermo-heating. Further investigations by in situ IR analysis and theoretical calculation provide comprehensive understanding of the reaction mechanism, and the important role of light is revealed. It is expected that the combination of catalysts and light may afford new perspectives for CO2 hydrogenation. © 2018 The Royal Society of Chemistry.
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英文
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Atomically manipulated proton transfer energizes water oxidation on silicon carbide photoanodes
作者：
Li, Hao;Shang, Huan;Shi, Yuchen;Yakimova, Rositsa;Syvajarvi, Mikael;...
期刊：
Journal of Materials Chemistry A ,2018年6(47):24358-24366 ISSN：2050-7488
通讯作者：
Sun, Jianwu
作者机构：
[Syvajarvi, Mikael; Shi, Yuchen; Li, Hao; Yakimova, Rositsa; Sun, Jianwu] Linkoping Univ, Dept Phys Chem & Biol, S-58183 Linkoping, Sweden.;[Zhang, Lizhi; Shang, Huan] Cent China Normal Univ, Coll Chem, Inst Appl & Environm Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Sun, Jianwu] L;Linkoping Univ, Dept Phys Chem & Biol, S-58183 Linkoping, Sweden.
摘要：
Surmounting the sluggish water oxidation kinetics beyond the hole-dominated thermodynamic effect is a topic of great scientific interest to establish fully renewable hydrogen technology from solar-powered water splitting. Herein, we demonstrate that the bottleneck of photoelectrochemical water oxidation can be overcome via atomic manipulation of proton transfer on the polar surfaces of silicon carbide (SiC) photoanodes. On the typical carbon-face SiC, where proton-coupled electron transfer governed the interfacial hole transfer for water oxidation, substantial energy loss was inevitable due to the highly activated proton-transfer steps. Via preferentially exposing the silicon-face, we enabled surface-catalyzed barrierless O-H breaking with a facile proton exchange and migration character. This mechanistically shifted the rate limiting step of water oxidation from sluggish proton-coupled electron transfer to a more energy-favorable electron transfer. The proof-of-concept study introduced here may open up new possibilities to design sophisticated photoelectrodes for an unbiased solar water splitting cell via surface engineering. © 2018 The Royal Society of Chemistry.
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英文
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Oxygen Vacancy-Mediated Photocatalysis of BiOCl: Reactivity, Selectivity, and Perspectives
作者：
Li, Hao;Li, Jie;Ai, Zhihui;Jia, Falong;Zhang, Lizhi*
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION ,2018年57(1):122-138 ISSN：1433-7851
通讯作者：
Zhang, Lizhi
作者机构：
[Zhang, Lizhi; Li, Hao; Li, Jie; Ai, Zhihui; Jia, Falong] Cent China Normal Univ, Coll Chem, Inst Environm Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
通讯机构：
[Zhang, Lizhi] C;Cent China Normal Univ, Coll Chem, Inst Environm Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
关键词：
BiOCl;nitrogen fixation;oxygen activation;photocatalysis;water splitting
摘要：
Semiconductor photocatalysis is a trustworthy approach to harvest clean solar light for energy conversions, while state-of-the-art catalytic efficiencies are unsatisfactory because of the finite light response and/or recombination of robust charge carriers. Along with the development of modern material characterization techniques and electronic-structure computations, oxygen vacancies (OVs) on the surface of real photocatalysts, even in infinitesimal concentration, are found to play a more decisive role in determining the kinetics, energetics, and mechanisms of photocatalytic reactions. This Review endeavors to clarify the inherent functionality of OVs in photocatalysis at the surface molecular level using 2D BiOCl as the platform. Structure sensitivity of OVs on reactivity and selectivity of photocatalytic reactions is intensely discussed via confining OVs onto prototypical BiOCl surfaces of different structures. The critical understanding of OVs chemistry can help consolidate and advance the fundamental theories of photocatalysis, and also offer new perspectives and guidelines for the rational design of catalysts with satisfactory performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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英文
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Molecular O2 Activation over Cu(I)-Mediated C=N Bond for Low-Temperature CO Oxidation
作者：
Hu, Siyu;Xiao, Wen;Yang, Weiwei;Yang, Ji;Fang, Yarong;...
期刊：
ACS Applied Materials & Interfaces ,2018年10(20):17167-17174 ISSN：1944-8244
通讯作者：
Guo, Yanbing
作者机构：
[Long, Juxia; Zhang, Lizhi; Deng, Hongtao; Luo, Zhu; Yang, Weiwei; Guo, Yanbing; Hu, Siyu; Yang, Ji; Fang, Yarong] Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.;[Ding, Jun; Xiao, Wen] Natl Univ Singapore, Dept Mat Sci & Engn, Singapore 117575, Singapore.
通讯机构：
[Guo, Yanbing] C;Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Hubei, Peoples R China.
关键词：
CO oxidation;CuTCNQ NWs;DFT calculations;in situ DRIFTS;molecular O2 activation
摘要：
The activation of molecular oxygen (O2) is extremely crucial in heterogeneous oxidations for various industrial applications. Here, a charge-transfer complex CuTCNQ nanowire (CuTCNQ NW) array grown on the copper foam was first reported to show CO catalytic oxidation activity at a temperature below 200 °C with the activated O2 as an oxidant. The molecular O2 was energetically activated over the Cu(I)-mediated C=N bond with a lower energy of -1.167 eV and preferentially reduced to •O2- through one-electron transfer during the activation process by density functional theory calculations and electron paramagnetic resonance. The theoretical calculations indicated that the CO molecule was oxidized by the activated O2 on the CuTCNQ NW surface via the Eley-Rideal mechanism, which had been further confirmed by in situ diffuse reflectance infrared Fourier transform spectra. These results indicated that the local C=N bond electron-state engineering could effectively improve the molecular O2 activation efficiency, which facilitates the low-temperature CO catalytic oxidation. The findings reported here enhance our understanding on the molecular oxygen activation pathway over metal-organic nanocatalysts and provide a new avenue for rational design of novel low-cost, organic-based heterogeneous catalysts. Copyright © 2018 American Chemical Society.
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