光-氧氧化预处理褐煤微生物降解效果提升的原因

预处理方法对煤的微生物降解效果影响较大,光-氧氧化预处理是一种具有应用前景的煤预处理方式,其在环保性和实际可操作性等方面具有一定的优越性。为探究经光-氧氧化预处理后,氧化煤微生物降解效果得到提升的原因,利用自制的旋转床光化学反应器对四种褐煤进行光-氧氧化预处理,并比较黄孢原毛平革菌对褐煤预处理前后的降解效果。通过元素分析、工业分析、红外光谱分峰拟合、定量分析、煤的比表面积分析和润湿性表征,探讨了煤在预处理前后的组成、结构特征和物理性质的变化。结果表明:黄孢原毛平革菌对四种光-氧氧化褐煤的降解效果均比原褐煤有较大幅度的提升;光-氧氧化褐煤的含氧量和含氢量增加,富氢程度和富氧程度增大,比表面积增大,润湿性增强,这些结构和性质的改变可能是黄孢原毛平革菌对光-氧氧化褐煤降解效果优于原煤的原因。

响应曲面法模拟优化细菌降解光-氧氧化褐煤工艺条件

在前期菌-煤匹配实验和单因素实验的基础上,选取恶臭假单胞菌降解光-氧氧化褐煤工艺条件中的加煤量、接种量和降解时间作为变量因素,以降解液在450 nm处的吸光度A450值作为响应值,进行三因素三水平的Box-Behnken设计,建立响应曲面模型对降解工艺条件进行模拟优化。结果表明:二次模型失拟项不显著,R^2=0.9990,可靠性高,能较好地模拟三个变量对响应值的影响;得出的最佳工艺条件为加煤量0.26 g/20 mL、接种量2.71 mL/20 mL、降解时间14.50 d,对应降解液的吸光度A450值为6.25687,验证实验的解液吸光度A450值为5.936,相对误差为5.12%,与模型预测值吻合度高。

真菌降解光-氧氧化内蒙古胜利褐煤产物分析

为掌握黄孢原毛平革菌降解光-氧氧化内蒙古胜利褐煤固体残渣的成分、结构和热稳定性的变化规律,以及降解液的主要物质构成,为降解工艺的改进以及降解产物的分离和利用提供参考,对降解所得的固体和液体产物进行了检测分析。结果表明:光-氧氧化煤被黄孢原毛平革菌作用后,煤残渣的水分、灰分和挥发分的质量分数均增加,固定碳的质量分数降低,由元素分析可见,煤残渣的O,N和H元素质量分数增加,C和S元素质量分数降低;煤残渣的富氢度增大、总脂芳比增大、富氧度增加,说明煤结构中的含O和H基团增加,芳环结构被降解而减少;煤残渣的稳定性比光-氧氧化煤的稳定性差,总失重率增大,进而说明光-氧氧化煤在黄孢原毛平革菌的作用下发生了降解;氧化煤在黄孢原毛平革菌的作用下,发生了明显的降解,降解液中含有丰富的芳香化合物,而培养基溶煤产物中芳香化合物的含量较少;降解液中含有丰富的化合物,主要为酯、烷烃和杂环化合物等。

真菌筛选及降解光-氧氧化褐煤工艺条件优化研究

为了获得降解褐煤的高效降解菌株,对五种真菌和四种光-氧氧化褐煤进行菌-煤匹配试验,筛选出的优势菌株为黄孢原毛平革菌。通过单因素试验探讨了黄孢原毛平革菌降解光-氧氧化内蒙古胜利褐煤的工艺条件,确定的较佳工艺条件为:加煤量为0.3 g/20 mL,接种量为1.5 mL/20 mL,降解时间为16 d,培养箱振荡频率为210 r/min,煤样粒度为-0.15+0.075 mm,降解温度为30℃;依此条件,研究了黄孢原毛平革菌对光-氧氧化云南昭通褐煤、光-氧氧化山西浑源褐煤和光-氧氧化内蒙古元宝山褐煤的降解效果,结果表明,此条件下,黄孢原毛平革菌对三种光-氧氧化褐煤的降解效果均有一定程度的提升。

Characteristics of Chlorophyll Fluorescence and Membrane-lipid Peroxidation of Various High-yield Rices Under Photooxidation Conditions

Using various high-yield rices (Oryza sativa L.) such as japonica cultivar 9516, two parental line hybrid rice between subspecies with more japonica element Peiai 64/E32, Liangyoupeijiu (Peiai 64/9311), and indica hybrid rices X07S/Zihui 100, Gangyou 881, Shanyou 63 as the materials, the characteristics of chlorophyll fluorescence and membrane-lipid peroxidation of detached leaves at booting stage under photooxidation conditions were studied. In comparison with indica hybrid rice, after the photooxidation treatment, the primary photochemical efficiency of PS II (F-v/F-m), quantum yield of linear electron transport of PS II (Phi(PSII)) and photochemical quenching coefficient (qP) in japonica cultivar and hybrid rice with japonica decreased less. This indicated that high-yield rice with japonica was able to maintain higher capability of light energy conversion, resulting in the alleviation of photoinhibition. Meanwhile, the higher activities of protective enzymes such as superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) led to the less accumulation of endogenous active oxygen (O-(2)(radical anion), H2O2) and less content of the malondialdehyde (MDA) and the less decline of chlorophyll and protein contents, indicating a stronger tolerance to photooxidation. The changes in contents of chlorophyll and protein among various nee cultivars during photooxidation treatment were consistent with the decline of chlorophyll content from heading stage to maturation stage under natural conditions. Statistical analysis showed that there was a significant correlation between the indexes of tolerance to photooxidation and the rate of seed setting, implying that the cultivar tolerated to photooxidation had higher resistance to early aging of leaf. These results suggested that from a view of superhigh-yield breeding, considering both the utilization of heterosis and the resistance to early aging of leaf, introduction of japonica element tolerating to photooxidation into the rice sterile line (maternal plant) is a breeding strategy worthy to pay great attention to.

Black TiO_2(B)/anatase bicrystalline TiO_(2-x) nanofibers with enhanced photocatalytic performance

Black TiO2（B）/anatase bicrystalline TiO2-x nanofibers were synthesized from a porous titanate derivative by calcination in H2, and were characterized using field-emission scanning electron microscopy, Raman spectroscopy, N2 adsorption-desorption analysis, X-ray photoelectron spectroscopy, thermogravimetric analysis, ultraviolet-visible diffuse reflection spectroscopy and photoluminescence measurements. Characterization results showed that no Ti3＋ was present on the surface of black bicrystalline TiO2-x and oxygen vacancies were distributed in the bulk of both TiO2（B） and anatase phases. The O/Ti atom stoichiometric ratio of black bicrystalline TiO2-x was estimated to be 1.97 from the difference of mass loss between black bicrystalline TiO2-x and white bicrystalline TiO2 without oxygen vacancies. The photocatalytic activity of black bicrystalline TiO2-x was 4.2 times higher than that of white bicrystalline TiO2 and 10.5 times higher than that of anatase TiOz. The high photocatalytic activity of black bicrystalline TiO2-x was attributed to its effective separation of electrons and holes, which may be related to the effects of both bicrystalline structure and oxygen vacancies. Black bicrystalline TiO2-x also exhibited good photocatalytic activity after recycling ten times. The black bicrystalline TiO2-x nanofibers show potential for use in environmental and energy applications.

Preparation of bismuth oxide/titania composite particles and their photocatalytic activity to degradation of 4-chlorophenol

Bismuth oxide/titania, one interfacial composite semiconductor with high photocatalytic activity under solar light, was prepared at low temperature. The structure was characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, brunauer-emmett-teller （BET）, X-ray photoelectron spectroscopy （XPS） and diffuse reflection spectra （DRS）. The results indicate that deposited titania nanoparticles on bismuth oxide surface have micro-nano structure, and this composite material exhibits porosity and increased surface hydroxyl groups. Furthermore, the as-prepared photocatalyst shows higher photocatalytic activity to the degradation of 4-chlorophenol than pure titania or P25 under sunlight.

Boosting CO_(2)photoreduction by synergistic optimization of multiple processes through metal vacancy engineering

The photoreduction of greenhouse gas CO_(2)using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2)photoreduction remains generally low due to the challenging activation of CO_(2)and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2)photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2)adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2)reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2)photoreduction and provides theoretical guidance for the development of novel CO_(2)photoreduction catalysts.

Synthesis of bionic-macro/microporous MgO-modified TiO_2 for enhanced CO_2 photoreduction into hydrocarbon fuels

The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O vapor into hydrocarbon fuel was studied with these MgO-TiO2 nanostructures as the photocatalysts with the benefits of improved CO2 adsorption and activation through incorporated MgO. Various factors involving CO2 adsorption capacity, migration of charge carriers to the surface, and the number of activity sites, which depend on the amount of added MgO, determine the photocatalytic conversion efficiency.

Enhanced visible-light photo-oxidation of nitric oxide using bismuth-coupled graphitic carbon nitride composite heterostructures

Pure bismuth（Bi） metal-modified graphitic carbon nitride（g-C3N4） composites（Bi-CN） with a pomegranate-like structure were prepared by an in situ method.The Bi-CN composites were used as photocatalysts for the oxidation of nitric oxide（NO） under visible-light irradiation.The inclusion of pure Bi metal in the g-C3N4 layers markedly improved the light absorption of the Bi-CN composites from the ultraviolet to the near-infrared region because of the typical surface plasmon resonance of Bi metal.The separation and transfer of photogenerated charge carriers were greatly accelerated by the presence of built-in Mott-Schottky effects at the interface between Bi metal and g-C3N4.As a result,the Bi-CN composite photocatalysts exhibited considerably enhanced efficiency in the photocatalytic removal of NO compared with that of Bi metal or g-C3N4 alone.The pomegranate-like structure of the Bi-CN composites and an explanation for their improved photocatalytic activity were proposed.This work not only provides a design for highly efficient g-C3N4-based photocatalysts through modification with Bi metal,but also offers new insights into the mechanistic understanding of g-C3N4-based photo catalysis.

Flower-like 3D CuO microsphere acting as photocatalytic water oxidation catalyst

Flower-like 3D CuO microspheres were synthesized and used to photo-catalyze water oxidation under visible light.The structure of the CuO microspheres was characterized by scanning electron microscopy,transmission electron microscopy,infrared,powder X-ray diffraction,electron dispersive spectroscopy,Raman and X-ray photoelectron spectroscopy（XPS）.This is the first time that a copper oxide was demonstrated as a photocatalytic water oxidation catalyst under near neutral conditions.The catalytic activity of CuO microspheres in borate buffer shows the best performance with O2 yield of 11.5%.No change in the surface properties of CuO before and after the photocatalytic reaction was seen by XPS,which showed good catalyst stability.A photocatalytic water oxidation reaction mechanism catalyzed by the CuO microspheres was proposed.

In situ synthesis of Ti^(3+) self-doped mesoporous TiO_2 as a durable photocatalyst for environmental remediation

This study developed a facile approach for in situ synthesis of a Ti3＋ self-doped mesoporous TiO 2photocatalyst by an evaporation-induced self-assembly method using TiC l3,water,and F127 as the titanium precursor,solvent,and soft template agent,respectively. The as-prepared samples were investigated by X-ray diffraction,N2 adsorption-desorption measurements,ultraviolet-visible diffuse reflectance spectroscopy,electron paramagnetic resonance,and transmission electron microscopy. The influence of different reaction parameters such as the dosage of F127 and calcination temperature on the photocatalytic performance of the resulting products was evaluated. The optimized product exhibited high photocatalytic activity and stability in the oxidation of nitric oxide in air and photocatalytic degradation of methylene blue. The excellent photocatalytic performance of the Ti3＋ self-doped mesoporous TiO 2 photocatalyst is attributed to the cooperation between the mesoporous structure and self-doped Ti3＋ enhancing light absorption and effectively suppressing the recombination of photogenerated electrons and holes.

Fabrication of a β-Bi_2O_3/BiOI heterojunction and its efficient photocatalysis for organic dye removal

To improve β-Bi2O3 photocatalysis,we couple β-Bi2O3 with BiO I to form β-Bi2O3/BiO I heterojunctions through an in-situ treatment with hydriodic acid. The prepared heterojunctions are characterized with X-ray diffraction,field emission scanning electron microscopy,transmission electron microscopy,ultra violet-diffuse reflectance spectroscopy,and X-ray photoelectron spectroscopy. Upon visible-light irradiation（λ 420 nm）,the β-Bi2O3/BiO I heterojunctions,especially with the molar ratio of HI to β-Bi2O3 at 0.4,exhibit much higher photocatalytic activity than pure β-Bi2O3 and BiO I for the degradation of methyl orange. The efficient separation of photogenerated electron-hole pairs across the interface of the heterojunction between β-Bi2O3 and BiO I would be responsible for the enhanced photocatalytic performances.

Fe-TiO_2 and Fe_2O_3 quantum dots co-loaded on MCM-41 for removing aqueous rose bengal by combined adsorption/photocatalysis

Adsorption and photodegradation are promising approaches for removing organic pollutions.In this study,we combined these two processes by co-loading Fe-TiO2 and Fe2O3 quantum dots(QDs)on porous MCM-41,using a simple hydrolysis method.X-ray diffraction,high-resolution transmission electron microscopy,and X-ray photoelectron spectroscopy results indicated that Fe-TiO2 QDs are formed at low Fe precursor concentrations,while additional Fe2O3 QDs are formed at higher Fe precursor concentrations.The Fe2O3 and Fe-TiO2 QDs impart high adsorption capacity and high photoactivity to the porous MCM-41,respectively.Thus,their combination results in a synergic effect of the adsorption and photodegradation.The highest-performing sample exhibits excellent performance in removing rose bengal from aqueous solution.

Microwave-assisted synthesis of defective tungsten trioxide for photocatalytic bacterial inactivation:Role of the oxygen vacancy

Surface defect modulation has emerged as a potential strategy for promoting the photocatalytic activity of photocatalysts for various applications, while the impact of the oxygen vacancy on bacterial inactivation is still debated. In this study, oxygen vacancies were introduced to tungsten trioxide nanosheets(WO3–x) via a microwave-assisted route. The as-prepared WO3–x nanosheets exhibited excellent visible-light-driven photocatalytic activity toward E. coli K-12 inactivation, and 6 log orders of the bacterial cells could be completely inactivated within 150 min. The obtained bacterial inactivation rate constant was 15.2 times higher than that of pristine WO3 without oxygen vacancies, suggesting that the surface oxygen vacancy could significantly promote the bacterial inactivation efficiency. The mechanism study indicated that the inactivation of bacterial cells occurs via a direct h+ oxidation pathway. In addition, the role of the oxygen vacancy was studied in detail;the oxygen vacancy was found to not only promote interfacial charge separation but also tune the band structure of WO3, thereby leading to increased h+ oxidation power. Finally, a possible oxygen vacancy-dominated photocatalytic bacterial inactivation mechanism is proposed. This work is expected to offer new insights into the microwave-assisted synthesis of defective photocatalysts and the use of the oxygen vacancy for promoting photocatalytic antibacterial activities.

Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO2

This work presents the visible-light photocatalytic selective oxidation of thiols to disulfides with molecular oxygen(O2) on anatase TiO2. The high specific surface area of anatase TiO2 proved to be especially critical in conferring high photocatalytic activity. Herein, surface complexation between thiol and TiO2 gives rise to photocatalytic activity under irradiation with 520 nm green light-emitting diodes(LEDs), resulting in excellent reaction activity, substrate scope, and functional group tolerance. The transformation was extremely efficient for the selective oxidation of various thiols, particularly with substrates bearing electron-withdrawing groups(reaction times of less than 10 min). To date, the longest wavelength of visible light that this system can utilize is 520 nm by the surface complex of substrate-TiO2. Importantly, O2 was found to act as the electron and proton acceptor, rather than to incorporate into the substrates. Our findings regarding this surface complex-based photocatalytic system can allow one to understand the interaction between the conduction band electrons and O2.

Synergetic effect between non-thermal plasma and photocatalytic oxidation on the degradation of gas-phase toluene: Role of ozone

In this study, a hybrid process using non‐thermal plasma (NTP) and photocatalytic oxidation (PCO) was adopted for the degradation of gas‐phase toluene using TiO2 as the photocatalyst. To discover the synergetic effect between NTP and PCO, the performances of both sole (O3, UV, NTP, and PCO) and combined (O3 + TiO2, O3 + UV, NTP + UV, O3 + PCO, and NTP + PCO) processes were investigated from different perspectives, such as the toluene removal efficiency, selectivity of COx, mineralization rate, ozone utilization, and the generation of by‐products. The toluene removal efficiency of the combined NTP + PCO process was 80.2%, which was much higher than that of a sole degradation process such as NTP (18.8%) and PCO (13.4%). The selectivity of CO2 and the ozone utilization efficiency also significantly improved. The amount of by‐products in the gas phase and the carbon‐ based intermediates adsorbed on the catalyst surface dramatically reduced. The improvement in the overall performances of the combined NTP + PCO process was mainly ascribed to the efficient utilization of ozone in the photocatalytic oxidation, and the ozone further acting as an electron acceptor and scavenger, generating more hydroxyl radicals and reducing the recombination of electron‐ hole pairs.

Enhanced visible-light photocatalytic degradation and disinfection performance of oxidized nanoporous g-C3N4 via decoration with graphene oxide quantum dots

Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO,as well as intimate contact with PCNO through hydrogen bonding,π-π,and chemical bonding interactions.In contrast with PCNO,the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability,higher charge-transfer efficiency,enhanced photooxidation capacity,and increased amounts of reactive species due to the upconversion properties,strong electron capturing ability,and peroxidase-like activity of the ox-GQDs.Therefore,the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced.Remarkably,the composite with a 0.2 wt.% deposited amount of ox-GQDs(ox-GQDs-0.2%/PCNO)exhibited optimum amaranth photodegradation activity,with a corresponding rate about 3.1 times as high as that of PCNO.In addition,ox-GQDs-0.2%/PCNO could inactivate about 99.6%of Escherichia coli(E.coli)cells after 4 h of visible light irradiation,whereas only^31.9% of E.coli cells were killed by PCNO.Furthermore,h+,·O2-,and·OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system;these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.

Robust photocatalytic benzene degradation using mesoporous disk-like N-TiO2 derived from MIL-125(Ti)

N-doped anatase-rutile titanium dioxide(N-TiO2)is a classical semiconductor widely used in environmental remediation.Its photocatalytic performance is typically affected by its morphology,porous structure,and phase composition.Herein,disk-like mesoporous N-TiO2 was prepared by calcining MIL-125(Ti)and melamine matrix at different temperatures in air.The photocatalytic efficiency of the prepared mesoporous N-TiO2 for the photo-oxidation of gaseous benzene under visible-light irradiation was studied.With respect to light absorption and mass transfer,as-prepared N-TiO2 annealed at 500℃(MM-500)showed the best photocatalytic activity with corresponding photodegradation and mineralization efficiencies of 99.1%and 72.0%,respectively.In addition.MM-500 exhibited excellent reusability and stability in cyclic experiments,in which 84.8%of gaseous benzene could still be photodegraded after 10 experimental cycles.Furthermore,electron spin resonance analysis indicated that·OH and·O2-radicals were the dominating reactive oxygen species during the photo-oxidation process.Their excellent performance suggests that the as-prepared N-TiO2 photocatalysts can be used to eliminate volatile organic compounds.

Effect of electron acceptors H_2O_2 and O_2 on the generated reactive oxygen species ~1O_2 and OH~· in TiO_2-catalyzed photocatalytic oxidation of glycerol

The effect of the electron acceptors H2O2 and O2 on the type of generated reactive oxygen species（ROS）,and glycerol conversion and product distribution in the TiO2-catalyzed photocatalytic oxidation of glycerol was studied at ambient conditions.In the absence of an electron acceptor,only HO^·radicals were generated by irradiated UV light and TiO2.However,in the presence of the two electron acceptors,both HO^· radical and ^1O2 were produced by irradiated UV light and TiO2 in different concentrations that depended on the concentration of the electron acceptor.The use of H2O2 as an electron acceptor enhanced glycerol conversion more than O2.The type of generated value-added compounds depended on the concentration of the generated ROS.