Porphyry Cu(Mo-Au)deposit is one of the most important types of copper deposit and usually formed under magmatic arc-related settings,whilst the Mujicun porphyry Cu-Mo deposit in North China Craton uncommonly generate...Porphyry Cu(Mo-Au)deposit is one of the most important types of copper deposit and usually formed under magmatic arc-related settings,whilst the Mujicun porphyry Cu-Mo deposit in North China Craton uncommonly generated within intra-continental settings.Although previous studies have focused on the age,origin and ore genesis of the Mujicun deposit,the ore-forming age,magma source and tectonic evolution remain controversial.Here,this study targeted rutile(TiO_(2))in the ore-hosting diorite porphyry from the Mujicun Cu-Mo deposit to conduct in situ U-Pb dating and trace element composition studies,with major views to determine the timing and magma evolution and to provide new insights into porphyry Cu-Mo metallogeny.Rutile trace element data show flat-like REE patterns characterized by relatively enrichment LREEs and depleted HREEs,which could be identified as magmatic rutile.Rutile U-Pb dating yields lower intercept ages of 139.3–138.4 Ma,interpreted as post magmatic cooling timing below about 500℃,which are consistent or slightly postdate with the published zircon U-Pb ages of diorite porphyry(144.1–141.7 Ma)and skarn(146.2 Ma;139.9 Ma)as well as the molybdenite Re-Os ages of molybdenum ores(144.8–140.0 Ma).Given that the overlap between the closure temperature of rutile U-Pb system and ore-forming temperature of the Mujicun deposit,this study suggests that the ore-forming ages of the Mujicun deposit can be constrained at 139.3–138.4 Ma,with temporal links to the late large-scale granitic magmatism at 138–126 Ma in the Taihang Orogen.Based on the Mg and Al contents in rutile,the magma of ore-hosting diorite porphyry was suggested to be derived from crust-mantle mixing components.In conjunction with previous studies in Taihang Orogen,this study proposes that the far-field effect and the rollback of the subducting Paleo-Pacific slab triggered lithospheric extension,asthenosphere upwelling,crust-mantle interaction and thermo-mechanical erosion,which jointly facilitated the formation of dioritic magmas during the Early Cretaceous.Subsequently,the dioritic magmas carrying crust-mantle mixing metallic materials were emplaced and precipitated at shallow positions along NNE-trending ore-controlling faults,eventually resulting in the formation of the Mujicun Cu-Mo deposit within an intracontinental extensional setting.展开更多
Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials.Carriers can interact with lattices and influence lattice vibrations;thus,it is feasible to study the ...Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials.Carriers can interact with lattices and influence lattice vibrations;thus,it is feasible to study the effect of photo-generated carriers on phonons by analyzing changes in the Raman spectra of semiconductors.Rutile is one of the predominant crystalline phases of TiO_(2),which is a widely utilized metal oxide semiconductor.In this work,rutile TiO_(2) is coated on a thinned optical fiber to concentrate ultraviolet light energy within the material,thereby enhancing the generation of carriers and amplifying the changes in the Raman spectra.A Raman detection laser with a wavelength of 532 nm is utilized to collect the Raman spectra of rutile TiO_(2) during irradiation.Using this setup,the impact of photo-generated carriers on the phonons corresponding to Raman vibrational modes is researched.The localization and non-radiative recombination of photo-generated carriers contribute to a reduction in both the frequencies and lifetimes of phonons.This work provides a novel approach to researching the effect of carriers on phonons.展开更多
The activity and adsorption behavior of oxygen on rutile TiO_(2)(110)(RTiO_(2)(110))were investigated using the temperature programmed desorption(TPD)method with methanol(CH_(3)OH)as the probe molecule.By controlling ...The activity and adsorption behavior of oxygen on rutile TiO_(2)(110)(RTiO_(2)(110))were investigated using the temperature programmed desorption(TPD)method with methanol(CH_(3)OH)as the probe molecule.By controlling the coverage of molecular O_(2) on the surface via increasing or decreasing O_(2) exposure,two chemisorbed O_(2)species on the surface are confirmed,one at the bridging oxygen vacancy(Ov)site(O_(2)^(2-)/Ov)and the other at the five-fold coordinated titanium(Ti_(5c))site(O^(2-)/Ti_(5c)).At low O_(2)exposure,O^(2-)/Ov is the main species on the surface,which only leads to the O-H bond cleavage of CH_(3)OH,producing methoxy groups(CHgO).However,after the Ov sites are nearly filled by O_(2) at about 0.1 L O_(2) exposure,O_(2)/Tisc species begins to appear on R-TiO_(2)(110)surface,resulting in the formation of formaldehyde(CH_(2)O)via the reaction of O_(2)/Tisc species with CH_(3)OH or CH3O to break the C-H bond at low surface temperature.Moreover,the yield of CH_(2)O increases linearly with that of H_(2)O.In addition,when the 1 L O_(2)covered surface is irradiated with 355 nm UV irradiation to desorb and dissociate O_(2)/Ti_(5c) species,the yield of CH_(2)O decreases linearly with that of H_(2)O.Further analysis suggests that the charge state of O_(2)/Ti_(5c) may not change as the exposure of O_(2)changes on the R-TiO_(2)(110) surface,and O_(2) is most likely to adsorb on the Ti_(5c)sites in the form of O_(2)^(2-),not O_(2)^(-),The result not only advances our understanding on the adsorption state of O_(2) on TiO_(2),but also provides clues for low temperature C-H bond activation with O_(2) on TiO_(2).展开更多
Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild c...Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild conditions,but the detailed reaction mechanism is not well understood.With the surface science approaches,we have studied the adsorption and surface chemistry of cyclohexane on rutile TiO_(2)(110).The thermal desorption spectroscopy and X-ray photoelectron spectroscopy results both demonstrate the molecular adsorption of cyclohexane on rutile TiO_(2)(110).Upon the UV Hg light irradiation,photodesorption of cyclohexane occurs from both the chemisorbed monolayer and the multilayer.No decomposition nor dehydrogenation of cyclohexane occurs on rutile TiO_(2)(110).These results deepen the fundamental understanding of the surface chemistry of cyclohexane on the TiO_(2) surface.展开更多
Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed wer...Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed were studied at 1173-1273 K. Thermodynamic analysis of this system revealed that the equation of producing CO was dominant at high temperatures. Based on the gas-solid multi-phase reaction theory and a two-phase model for the fluidized bed, the mathematical description for the chlorination reaction of rutile was proposed. The reaction parameters and the average concentration of gaseous chlorine in the emulsion phase were estimated. The average concentration of emulsion phase in the range of fluidized bed was calculated as 0.3 mol/m^3. The results showed that the chlorination of natural rutile proceeded principally in the emulsion phase, and the reaction rate was mainly controlled by the surface reaction.展开更多
A new technique was developed for the conversion of high titania slag,containing 70%-75% TiO2 and with MgO,FeO,CaO,Al2O3 and SiO2 as main impurities,into a synthetic rutile,90%-95% TiO2,which satisfies the requirement...A new technique was developed for the conversion of high titania slag,containing 70%-75% TiO2 and with MgO,FeO,CaO,Al2O3 and SiO2 as main impurities,into a synthetic rutile,90%-95% TiO2,which satisfies the requirements for fluidizing chlorination process with respect to impurity contents.After a pre-oxidation at around 1 042 ℃ and a heat-treatment above 1 510 ℃,the Ti components in high titania slag can be enriched into the rutile phase which can precipitate and grow,and can be separated with dilute hydrochloric and sulfuric acid,respectively.The results show that the average crystal size of rutile phase is over 25 μm,and the synthetic rutile containing more than 95% TiO2 can be produced by selective leaching.展开更多
The original strain HY-7 was isolated from the bauxite mine drainage（BMD） taken from a reservoir in Sanmenxia Mine,Henan Province,China.The optimum temperature and pH for the growth of strain HY-7 were 30 ℃ and 7.0...The original strain HY-7 was isolated from the bauxite mine drainage（BMD） taken from a reservoir in Sanmenxia Mine,Henan Province,China.The optimum temperature and pH for the growth of strain HY-7 were 30 ℃ and 7.0,respectively.The optimum UV radiating time was 20 s and the positive mutation rate was 23.0%.The growth curves show that strain HY-7 needs144 h to reach the stationary phase after its mutagenesis,which is 24 h earlier than that of the original strain.Sequence homology analysis indicated that this community consisted of mainly two branches：one sharing high homology with Paenibacillus stellifer and the other sharing high homology with Sporolactobacillus laevolacticus.The experimental results showed that the TiO2 grade of mtile concentrate increased from 78.21%to 91.80%and the recovery of TiO2 reached 95.24%after 7 d of bioleaching.The bio-desilication process can not only effectively improve the TiO2 grade of rutile concentrate but also meet the requirements of environmental protection.展开更多
Junctions are an important structure that allows charge separation in solar cells and photocatalysts. Here, we studied the charge transfer at an anatase/rutile TiO2 phase junction using time-resolved photoluminescence...Junctions are an important structure that allows charge separation in solar cells and photocatalysts. Here, we studied the charge transfer at an anatase/rutile TiO2 phase junction using time-resolved photoluminescence spectroscopy. Visible （-S00 nm） and near-infrared （NIR, -830 nm） emissions were monitored to give insight into the photoinduced charges of anatase and rutile in the junction, respectively, New fast photoluminescence decay components appeared in the visible emission of futile-phase dominated TiO2 and in the NIR emission of many mixed phase TiO2samples. The fast decays confirmed that the charge separation occurred at the phase junction. The visible emission intensity from the mixed phase TiO2 increased, revealing that charge transfer from rutile to anatase was the main pathway. The charge separation slowed the microsecond time scale photolumines- cence decay rate for charge carriers in both anatase and rutile. However, the millisecond decay of the charge carriers in anatase TiO2 was accelerated, while there was almost no change in the charge carrier dynamics of rutile TiO2. Thus, charge separation at the anatase/rutile phase junction caused an increase in the charge carrier concentration on a microsecond time scale, because of slower electron-hole recombination. The enhanced photocatalytic activity previously observed at ana- tase/rutile phase junctions is likely caused by the improved charge carrier dynamics we report here. These findings may contribute to the development of improved photocatalytic materials.展开更多
The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectro...The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy（XPS）. According to the results of micro-flotation, Bi（Ⅲ） ions could largely improve the rutile flotation recovery（from 62% to 91%）, and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH-ions, which determined that Bi（Ⅲ） ions were capable of activating rutile flotation. The adsorption of Bi（Ⅲ） ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi（Ⅲ） ions. Based on the adsorption mechanism of Bi（Ⅲ） ions, it was deduced that firstly Bi（Ⅲ） ions occupied the vacancies of the original Ca^2＋, Mg^2＋ and Fe^2＋ ions on the rutile surface; secondly Bi（Ⅲ） ions covered on the rutile surface in the form of hydroxides.展开更多
The hydrophobic flocculation flotation of rutile fines in the presence of styryl phosphonic acid（SPA） was investigated by flotation tests, zeta-potential measurement, optical microscope observation, laser-based part...The hydrophobic flocculation flotation of rutile fines in the presence of styryl phosphonic acid（SPA） was investigated by flotation tests, zeta-potential measurement, optical microscope observation, laser-based particle size analysis, adsorption measurements and DLVO theory. The flotation tests indicated that rutile fines could be flocculated by SPA, and pH, shear force（stirring speed） and stirring time played significant roles in flocculation. The isoelectric point（IEP） and zeta-potential in whole range all moved to negative values as SPA was added according to the results from zeta-potential measurement. It was demonstrated that the primary reason for above was chemical adsorption. The laser-based particle size results showed the particle size at a stirring speed of 1800 r/min and 1000 mg/L SPA was the largest in all experiments. Furthermore, using the optical microscope observation and flotation tests, it was important for flotation of rutile fines to produce the flocculant. In the light of above-mentioned facts, floc flotation of rutile fines could be induced in the form of chemical adsorption by SPA to increase particle size. The data calculated from DLVO theory also indicated that chemical adsorption was the main reason for the formation of flocculant.展开更多
In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successf...In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.展开更多
In this paper, the thermodynamics and kinetics of nature rutile carbochlorination in a fluidized-bed were investigated. The thermodynamic calculations of TiO2-C- C12 system show that when C is excess in the solid phas...In this paper, the thermodynamics and kinetics of nature rutile carbochlorination in a fluidized-bed were investigated. The thermodynamic calculations of TiO2-C- C12 system show that when C is excess in the solid phase, titanium tetrachloride and carbon monoxide can exist sta- bly. At high temperature, the reaction with CO as the product is the dominant reaction. The appropriate reaction conditions are as follows： reaction temperature of 950 ℃, reaction time of 40 min, carbon ratio of 30 wt% of rutile, natural rutile particle size of -96 μm, petroleum coke size of -150 μm, and chlorine flow of 0.036 m3.h-1. Under the above conditions, the reaction conversion rate of TiO2 can reach about 95 %. This paper proposed a reaction rate model, and got a rutile chlorination rate formula, which is generally consistent with the experimental data. For the TiO2-C-C12 system, the reaction rate is dependent on the initial radius of rutile particle, density, and the partial pressures of C12. From 900 to 1,000 ℃, the apparent activation energy is 10.569 kJ.mo1-1, and the mass diffu- sion is found to be the main reaction-controlling step. The expression for the chlorine reaction rate in the C-C12 sys- tem is obtained, and it depends on the degree of reaction, the partial pressure of C12, and the size of rutile particle.展开更多
The effect of rutile crystal shapes on its settlement in a modified slag was studied by theoretical analysis,FactSage simulation,X-ray diffraction and scanning electron microscopy.The results show that the settling ve...The effect of rutile crystal shapes on its settlement in a modified slag was studied by theoretical analysis,FactSage simulation,X-ray diffraction and scanning electron microscopy.The results show that the settling velocities of spherical rutile crystals are faster than those of other shapes of rutile crystals under the same volume conditions,and the shape transformation of rutile crystals from rod to sphere can be achieved by adding titanium slag to Ti-bearing blast furnace slag.The volume fractions of the rutile crystals in the upper and lower parts of the modified slag are 30%and 71%when the added titanium slag increases to 278 g,indicating that rutile settling is obvious.Due to the rutile settling,half shaker sorting task is saved,and the recovery rate of TiO2 is significantly increased.The TiO2 content of rutile is greater than 93%,and the total content of CaO and MgO is less than 0.4%,meeting the requirements for the raw materials of titanium white in the chloride process.展开更多
This paper describes a novel, facile chemical pathway for preparing synthetic rutile from ilmenite. The pathway consists of two primary units, i.e., selectively sulfating ilmenite, which was realized via roasting ilme...This paper describes a novel, facile chemical pathway for preparing synthetic rutile from ilmenite. The pathway consists of two primary units, i.e., selectively sulfating ilmenite, which was realized via roasting ilmenite with(NH_4)_2SO_4followed by selective thermal decomposition of the sulfated ilmenite, and targeted leaching of the impurities. The effects of the process parameters were systematically investigated. The results showed that the optimum sulfation conditions were a mass ratio of(NH_4)_2SO_4to ilmenite of 14, temperature of 360 °C, and time of 120 min with a sulfation ratio of ~ 95%. The optimum thermal decomposition conditions were480 °C in N_2 atmosphere, and nearly all Ti OSO_4 were decomposed with co-decomposition of Fe SO_4 of 23%. For acid leaching, the optimum conditions were 2.5 wt% HCl, 98 °C and 120 min. Under those conditions, 94.2% iron was removed with a Ti O_2 dissolution loss b 1%. For alkali leaching, 67% Si O_2 was removed in 5 wt% Na OH at102 °C for 1 h. A synthetic rutile with a Ti O_2 content N 92 wt% and total Mg O + Ca O b 1.5 wt% was obtained.Based on these results, a schematic flowsheet was proposed. Additionally, it was found that the decomposition of Fe SO_4 mixed with Ti OSO_4 under N_2was inhibited due to its oxidation to a higher thermal stability Fe_2(SO_4)_3by oxygen emitted from the decomposition of Ti OSO_4. At the same time, Ti OSO_4 decomposition was promoted due to the immediate in situ consumption of oxygen by Fe SO_4. The synergetic effect might be responsible for the enhanced selectivity of sulfated ilmenite thermal decomposition.展开更多
A reagent combination of sodium oleate(NaOl)and salicyl hydroximic acid was employed as the roughing and scavenging collectors,whereas styryl phosphoric acid(SPA)and octanol were employed as the cleaning collectors.Re...A reagent combination of sodium oleate(NaOl)and salicyl hydroximic acid was employed as the roughing and scavenging collectors,whereas styryl phosphoric acid(SPA)and octanol were employed as the cleaning collectors.Results of bench-scale flotation demonstrate that the dosage of SPA can be reduced by about 80%,and that a better flotation index can be obtained using the proposed reagent system.The results of adsorption amount and contact angle measurements indicate that the rutile surface adsorbed not only a large amount of residual NaOl but also SPA and a small amount of NaOl remained on the amphibole surface in strong acidic solution.The hydrophobic difference between rutile and amphibole surfaces was therefore amplified in cleaning,and their further separation became much easier consequently.展开更多
The separation of rutile from apatite by flotation and the mechanism of depressing the apatite of sodium hexametaphosphate were studied. The results showed that rutile and apatite could be separated by using alkyl-imi...The separation of rutile from apatite by flotation and the mechanism of depressing the apatite of sodium hexametaphosphate were studied. The results showed that rutile and apatite could be separated by using alkyl-imino-bismethylene phosphoric acid and sodium hexametaphosphate as a collector and a regulator, respectively. Sodium hexametaphosphate could selectively dissolve calcium ions on the apatite surface, and make calcium ions break away from lattice binding through combining.展开更多
TiO2 nanowire arrays were successfully fabricated by liquid-phase deposition method using porous alumina templates. The obtained TiO2 nanowires were characterized using Raman spectroscopy, X-ray diffraction （XRD）, s...TiO2 nanowire arrays were successfully fabricated by liquid-phase deposition method using porous alumina templates. The obtained TiO2 nanowires were characterized using Raman spectroscopy, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, field emission scanning electron microscopy （FE- SEM）, transmission electron microscopy （TEM）, and selected area electron diffraction （SAED） analysis. Results of electron microscopic observations indicated that the nanowires were smooth and uniform with a diameter of about 50-80 nm and several micrometers in length. SAED, Raman, and XRD mea- surements showed that TiO2 nanowires were single-crystalline with a pure rutile structure after heating at 800 ~C for 10 h. In this situation, the nanowire constituents grew preferentially along the 〈001〉 direction. Furthermore, the formation process and mechanistic study of the Ti02 nanowire arrays were proposed and discussed in detail. The nanowires are clearly produced by the deposition of TiO2 particles on the inner wall of the template nanochannels.展开更多
A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activi...A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a futile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80：20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.展开更多
We report the discovery of TiO_(2)-Ⅱ in the unmelted rock of the shocked Suizhou L6 chondrite.Natural TiO_(2)-Ⅱ was previously found in ultrahigh-pressure metamorphic and mantle-derived rocks,terrestrial impact stru...We report the discovery of TiO_(2)-Ⅱ in the unmelted rock of the shocked Suizhou L6 chondrite.Natural TiO_(2)-Ⅱ was previously found in ultrahigh-pressure metamorphic and mantle-derived rocks,terrestrial impact structures,and tektite.Our microscopic,Raman spectroscopic,electron microprobe and transmission electron microscopic investigations have revealed:(1) All observed TiO_(2)-Ⅱ grains are related with ilmenite and pyrophanite;(2) TiO_(2)-Ⅱ occurs as needle-and leaf-shaped inclusions in llmenite and patch-,tape-shaped body in pyrophanite;(3)The composition of TiO_(2)-Ⅱ is identical with that of its precursor rutile;(4) The Raman spectrum of TiO_(2)-Ⅱ is in good agreement with that of natural and synthesized α-PbO_(2)-type TiO_(2);(5) TiO_(2)-Ⅱ occurs mainly in the form of well-ordered nano-domains and small mis-orientation among the domains can be observed.(6) All electron diffraction reflections from TiO_(2)-Ⅱ can be indexed to α-PbO_(2)structure in space group Pbcn with lattice parameters of a=4.481 ?,b=5.578 A and c=4.921 A;(7) The exsolution inclusions of rutile from host ilmenite are mostly connected with an alternation process along the lamellar twinning plane of ilmenite induced by shockinduced high pressure and high temperature;(8) The P-T regime of 20-25 GPa and 1000 ℃ estimated for the Suizhou unmelted rock is suitable for phase transition of rutile into TiO_(2)-Ⅱ phase.展开更多
基金jointly supported by the National Natural Science Foundation of China(4220207742103025)+5 种基金the Opening Foundation of MNR Key Laboratory of Metallogeny and Mineral Assessment(ZS2209ZS2106)the Opening Foundation of Key Laboratory of Mineral Resources in Western China(Gansu Province)(MRWCGS-2021-01)the Natural Science Foundation of Gansu Province(22JR5RA440)the Fundamental Research Funds for the Central Universities(LZUJBKY-2022-42)the Guiding Special Funds of“Double First-Class(First-Class University&First-Class Disciplines)”(561119201)of Lanzhou University,China。
文摘Porphyry Cu(Mo-Au)deposit is one of the most important types of copper deposit and usually formed under magmatic arc-related settings,whilst the Mujicun porphyry Cu-Mo deposit in North China Craton uncommonly generated within intra-continental settings.Although previous studies have focused on the age,origin and ore genesis of the Mujicun deposit,the ore-forming age,magma source and tectonic evolution remain controversial.Here,this study targeted rutile(TiO_(2))in the ore-hosting diorite porphyry from the Mujicun Cu-Mo deposit to conduct in situ U-Pb dating and trace element composition studies,with major views to determine the timing and magma evolution and to provide new insights into porphyry Cu-Mo metallogeny.Rutile trace element data show flat-like REE patterns characterized by relatively enrichment LREEs and depleted HREEs,which could be identified as magmatic rutile.Rutile U-Pb dating yields lower intercept ages of 139.3–138.4 Ma,interpreted as post magmatic cooling timing below about 500℃,which are consistent or slightly postdate with the published zircon U-Pb ages of diorite porphyry(144.1–141.7 Ma)and skarn(146.2 Ma;139.9 Ma)as well as the molybdenite Re-Os ages of molybdenum ores(144.8–140.0 Ma).Given that the overlap between the closure temperature of rutile U-Pb system and ore-forming temperature of the Mujicun deposit,this study suggests that the ore-forming ages of the Mujicun deposit can be constrained at 139.3–138.4 Ma,with temporal links to the late large-scale granitic magmatism at 138–126 Ma in the Taihang Orogen.Based on the Mg and Al contents in rutile,the magma of ore-hosting diorite porphyry was suggested to be derived from crust-mantle mixing components.In conjunction with previous studies in Taihang Orogen,this study proposes that the far-field effect and the rollback of the subducting Paleo-Pacific slab triggered lithospheric extension,asthenosphere upwelling,crust-mantle interaction and thermo-mechanical erosion,which jointly facilitated the formation of dioritic magmas during the Early Cretaceous.Subsequently,the dioritic magmas carrying crust-mantle mixing metallic materials were emplaced and precipitated at shallow positions along NNE-trending ore-controlling faults,eventually resulting in the formation of the Mujicun Cu-Mo deposit within an intracontinental extensional setting.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.52122008,51978024,and 52370003)the Science and Technology and Innovation Commission of Shen Zhen Municipality(Grant No.JCYJ20200109105212568).
文摘Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials.Carriers can interact with lattices and influence lattice vibrations;thus,it is feasible to study the effect of photo-generated carriers on phonons by analyzing changes in the Raman spectra of semiconductors.Rutile is one of the predominant crystalline phases of TiO_(2),which is a widely utilized metal oxide semiconductor.In this work,rutile TiO_(2) is coated on a thinned optical fiber to concentrate ultraviolet light energy within the material,thereby enhancing the generation of carriers and amplifying the changes in the Raman spectra.A Raman detection laser with a wavelength of 532 nm is utilized to collect the Raman spectra of rutile TiO_(2) during irradiation.Using this setup,the impact of photo-generated carriers on the phonons corresponding to Raman vibrational modes is researched.The localization and non-radiative recombination of photo-generated carriers contribute to a reduction in both the frequencies and lifetimes of phonons.This work provides a novel approach to researching the effect of carriers on phonons.
基金This work was supported by the National Natural Science Foundation of China(No.21973010)Liaoning Revitalization Talents Program(No.XLYC1907032)The authors thank Qing Guo at Southern University of Science and Technolog for many insightful discussions。
文摘The activity and adsorption behavior of oxygen on rutile TiO_(2)(110)(RTiO_(2)(110))were investigated using the temperature programmed desorption(TPD)method with methanol(CH_(3)OH)as the probe molecule.By controlling the coverage of molecular O_(2) on the surface via increasing or decreasing O_(2) exposure,two chemisorbed O_(2)species on the surface are confirmed,one at the bridging oxygen vacancy(Ov)site(O_(2)^(2-)/Ov)and the other at the five-fold coordinated titanium(Ti_(5c))site(O^(2-)/Ti_(5c)).At low O_(2)exposure,O^(2-)/Ov is the main species on the surface,which only leads to the O-H bond cleavage of CH_(3)OH,producing methoxy groups(CHgO).However,after the Ov sites are nearly filled by O_(2) at about 0.1 L O_(2) exposure,O_(2)/Tisc species begins to appear on R-TiO_(2)(110)surface,resulting in the formation of formaldehyde(CH_(2)O)via the reaction of O_(2)/Tisc species with CH_(3)OH or CH3O to break the C-H bond at low surface temperature.Moreover,the yield of CH_(2)O increases linearly with that of H_(2)O.In addition,when the 1 L O_(2)covered surface is irradiated with 355 nm UV irradiation to desorb and dissociate O_(2)/Ti_(5c) species,the yield of CH_(2)O decreases linearly with that of H_(2)O.Further analysis suggests that the charge state of O_(2)/Ti_(5c) may not change as the exposure of O_(2)changes on the R-TiO_(2)(110) surface,and O_(2) is most likely to adsorb on the Ti_(5c)sites in the form of O_(2)^(2-),not O_(2)^(-),The result not only advances our understanding on the adsorption state of O_(2) on TiO_(2),but also provides clues for low temperature C-H bond activation with O_(2) on TiO_(2).
基金This work is supported by the National Natural Science Foundation of China(No.22202191).
文摘Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild conditions,but the detailed reaction mechanism is not well understood.With the surface science approaches,we have studied the adsorption and surface chemistry of cyclohexane on rutile TiO_(2)(110).The thermal desorption spectroscopy and X-ray photoelectron spectroscopy results both demonstrate the molecular adsorption of cyclohexane on rutile TiO_(2)(110).Upon the UV Hg light irradiation,photodesorption of cyclohexane occurs from both the chemisorbed monolayer and the multilayer.No decomposition nor dehydrogenation of cyclohexane occurs on rutile TiO_(2)(110).These results deepen the fundamental understanding of the surface chemistry of cyclohexane on the TiO_(2) surface.
基金Projects(51374064,51004033,51074044)supported by the National Natural Science Foundation of ChinaProject(2012AA062303)supported by High-tech Research and Development Program of China
文摘Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed were studied at 1173-1273 K. Thermodynamic analysis of this system revealed that the equation of producing CO was dominant at high temperatures. Based on the gas-solid multi-phase reaction theory and a two-phase model for the fluidized bed, the mathematical description for the chlorination reaction of rutile was proposed. The reaction parameters and the average concentration of gaseous chlorine in the emulsion phase were estimated. The average concentration of emulsion phase in the range of fluidized bed was calculated as 0.3 mol/m^3. The results showed that the chlorination of natural rutile proceeded principally in the emulsion phase, and the reaction rate was mainly controlled by the surface reaction.
基金Project(FMRU2007K10)supported by the Open Research Fund of Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education,China
文摘A new technique was developed for the conversion of high titania slag,containing 70%-75% TiO2 and with MgO,FeO,CaO,Al2O3 and SiO2 as main impurities,into a synthetic rutile,90%-95% TiO2,which satisfies the requirements for fluidizing chlorination process with respect to impurity contents.After a pre-oxidation at around 1 042 ℃ and a heat-treatment above 1 510 ℃,the Ti components in high titania slag can be enriched into the rutile phase which can precipitate and grow,and can be separated with dilute hydrochloric and sulfuric acid,respectively.The results show that the average crystal size of rutile phase is over 25 μm,and the synthetic rutile containing more than 95% TiO2 can be produced by selective leaching.
基金Project(2011-622-40)supported by the Mineral Exploration Foundation of Henan Province,ChinaProject(51104189)supported by the National Natural Science Foundation of ChinaProject(2013M531814)supported by the 53rd China Postdoctoral Science Foundation
文摘The original strain HY-7 was isolated from the bauxite mine drainage（BMD） taken from a reservoir in Sanmenxia Mine,Henan Province,China.The optimum temperature and pH for the growth of strain HY-7 were 30 ℃ and 7.0,respectively.The optimum UV radiating time was 20 s and the positive mutation rate was 23.0%.The growth curves show that strain HY-7 needs144 h to reach the stationary phase after its mutagenesis,which is 24 h earlier than that of the original strain.Sequence homology analysis indicated that this community consisted of mainly two branches：one sharing high homology with Paenibacillus stellifer and the other sharing high homology with Sporolactobacillus laevolacticus.The experimental results showed that the TiO2 grade of mtile concentrate increased from 78.21%to 91.80%and the recovery of TiO2 reached 95.24%after 7 d of bioleaching.The bio-desilication process can not only effectively improve the TiO2 grade of rutile concentrate but also meet the requirements of environmental protection.
基金supported by the National Natural Science Foundation of China (21203185, 21373209)the National Basic Research Program of China (2014CB239400)
文摘Junctions are an important structure that allows charge separation in solar cells and photocatalysts. Here, we studied the charge transfer at an anatase/rutile TiO2 phase junction using time-resolved photoluminescence spectroscopy. Visible （-S00 nm） and near-infrared （NIR, -830 nm） emissions were monitored to give insight into the photoinduced charges of anatase and rutile in the junction, respectively, New fast photoluminescence decay components appeared in the visible emission of futile-phase dominated TiO2 and in the NIR emission of many mixed phase TiO2samples. The fast decays confirmed that the charge separation occurred at the phase junction. The visible emission intensity from the mixed phase TiO2 increased, revealing that charge transfer from rutile to anatase was the main pathway. The charge separation slowed the microsecond time scale photolumines- cence decay rate for charge carriers in both anatase and rutile. However, the millisecond decay of the charge carriers in anatase TiO2 was accelerated, while there was almost no change in the charge carrier dynamics of rutile TiO2. Thus, charge separation at the anatase/rutile phase junction caused an increase in the charge carrier concentration on a microsecond time scale, because of slower electron-hole recombination. The enhanced photocatalytic activity previously observed at ana- tase/rutile phase junctions is likely caused by the improved charge carrier dynamics we report here. These findings may contribute to the development of improved photocatalytic materials.
基金Project(51474254)supported by the National Natural Science Foundation of ChinaProject(2013M531813)supported by the China Postdoctoral Science Foundation+1 种基金Project(2016zzts111)supported by the Independent Exploration and Innovation Program of Central South University,ChinaProject(CSUZC201715)supported by Open-End Fund for the Valuable and Precision Instruments of Central South University,China
文摘The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy（XPS）. According to the results of micro-flotation, Bi（Ⅲ） ions could largely improve the rutile flotation recovery（from 62% to 91%）, and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH-ions, which determined that Bi（Ⅲ） ions were capable of activating rutile flotation. The adsorption of Bi（Ⅲ） ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi（Ⅲ） ions. Based on the adsorption mechanism of Bi（Ⅲ） ions, it was deduced that firstly Bi（Ⅲ） ions occupied the vacancies of the original Ca^2＋, Mg^2＋ and Fe^2＋ ions on the rutile surface; secondly Bi（Ⅲ） ions covered on the rutile surface in the form of hydroxides.
基金Projects(51474254,51774332,51320105006) supported by the National Natural Science Foundation of ChinaProject(NCET-13-0595) supported by the Program for New Century Excellent Talents in University,ChinaProjects(2017zzts579,2017zzts379) supported by the Fundamental Research Funds for the Central Universities of China
文摘The hydrophobic flocculation flotation of rutile fines in the presence of styryl phosphonic acid（SPA） was investigated by flotation tests, zeta-potential measurement, optical microscope observation, laser-based particle size analysis, adsorption measurements and DLVO theory. The flotation tests indicated that rutile fines could be flocculated by SPA, and pH, shear force（stirring speed） and stirring time played significant roles in flocculation. The isoelectric point（IEP） and zeta-potential in whole range all moved to negative values as SPA was added according to the results from zeta-potential measurement. It was demonstrated that the primary reason for above was chemical adsorption. The laser-based particle size results showed the particle size at a stirring speed of 1800 r/min and 1000 mg/L SPA was the largest in all experiments. Furthermore, using the optical microscope observation and flotation tests, it was important for flotation of rutile fines to produce the flocculant. In the light of above-mentioned facts, floc flotation of rutile fines could be induced in the form of chemical adsorption by SPA to increase particle size. The data calculated from DLVO theory also indicated that chemical adsorption was the main reason for the formation of flocculant.
基金supported by the National Natural Science Foundation of China (21771070, 21571071)the Fundamental Research Funds for the Central Universities (2018KFYYXJJ120, 2019KFYRCPY104)~~
文摘In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.
基金financially supported by the National Natural Science Foundation of China(Nos.51374064,51004033,and 51074044)the National High-Tech Research and Development Program of China(No.2012AA062303)+1 种基金the National Key Technology Support Program during the 12th Five-Year Plan Period(No.2012BAE01B02)the Fundamental Research Funds for the Central Universities(Nos.N130402012 and N130702001)
文摘In this paper, the thermodynamics and kinetics of nature rutile carbochlorination in a fluidized-bed were investigated. The thermodynamic calculations of TiO2-C- C12 system show that when C is excess in the solid phase, titanium tetrachloride and carbon monoxide can exist sta- bly. At high temperature, the reaction with CO as the product is the dominant reaction. The appropriate reaction conditions are as follows： reaction temperature of 950 ℃, reaction time of 40 min, carbon ratio of 30 wt% of rutile, natural rutile particle size of -96 μm, petroleum coke size of -150 μm, and chlorine flow of 0.036 m3.h-1. Under the above conditions, the reaction conversion rate of TiO2 can reach about 95 %. This paper proposed a reaction rate model, and got a rutile chlorination rate formula, which is generally consistent with the experimental data. For the TiO2-C-C12 system, the reaction rate is dependent on the initial radius of rutile particle, density, and the partial pressures of C12. From 900 to 1,000 ℃, the apparent activation energy is 10.569 kJ.mo1-1, and the mass diffu- sion is found to be the main reaction-controlling step. The expression for the chlorine reaction rate in the C-C12 sys- tem is obtained, and it depends on the degree of reaction, the partial pressure of C12, and the size of rutile particle.
基金Project(2015BAB18B00)supported by the National Science and Technology Support Program of China。
文摘The effect of rutile crystal shapes on its settlement in a modified slag was studied by theoretical analysis,FactSage simulation,X-ray diffraction and scanning electron microscopy.The results show that the settling velocities of spherical rutile crystals are faster than those of other shapes of rutile crystals under the same volume conditions,and the shape transformation of rutile crystals from rod to sphere can be achieved by adding titanium slag to Ti-bearing blast furnace slag.The volume fractions of the rutile crystals in the upper and lower parts of the modified slag are 30%and 71%when the added titanium slag increases to 278 g,indicating that rutile settling is obvious.Due to the rutile settling,half shaker sorting task is saved,and the recovery rate of TiO2 is significantly increased.The TiO2 content of rutile is greater than 93%,and the total content of CaO and MgO is less than 0.4%,meeting the requirements for the raw materials of titanium white in the chloride process.
基金Supported by the National Key Projects for Fundamental Research and Development of China(2016YFB0600904)
文摘This paper describes a novel, facile chemical pathway for preparing synthetic rutile from ilmenite. The pathway consists of two primary units, i.e., selectively sulfating ilmenite, which was realized via roasting ilmenite with(NH_4)_2SO_4followed by selective thermal decomposition of the sulfated ilmenite, and targeted leaching of the impurities. The effects of the process parameters were systematically investigated. The results showed that the optimum sulfation conditions were a mass ratio of(NH_4)_2SO_4to ilmenite of 14, temperature of 360 °C, and time of 120 min with a sulfation ratio of ~ 95%. The optimum thermal decomposition conditions were480 °C in N_2 atmosphere, and nearly all Ti OSO_4 were decomposed with co-decomposition of Fe SO_4 of 23%. For acid leaching, the optimum conditions were 2.5 wt% HCl, 98 °C and 120 min. Under those conditions, 94.2% iron was removed with a Ti O_2 dissolution loss b 1%. For alkali leaching, 67% Si O_2 was removed in 5 wt% Na OH at102 °C for 1 h. A synthetic rutile with a Ti O_2 content N 92 wt% and total Mg O + Ca O b 1.5 wt% was obtained.Based on these results, a schematic flowsheet was proposed. Additionally, it was found that the decomposition of Fe SO_4 mixed with Ti OSO_4 under N_2was inhibited due to its oxidation to a higher thermal stability Fe_2(SO_4)_3by oxygen emitted from the decomposition of Ti OSO_4. At the same time, Ti OSO_4 decomposition was promoted due to the immediate in situ consumption of oxygen by Fe SO_4. The synergetic effect might be responsible for the enhanced selectivity of sulfated ilmenite thermal decomposition.
基金Projects(11575281,11290165,11305252,U1532260,51474254)supported by the National Natural Science Foundation of China
文摘A reagent combination of sodium oleate(NaOl)and salicyl hydroximic acid was employed as the roughing and scavenging collectors,whereas styryl phosphoric acid(SPA)and octanol were employed as the cleaning collectors.Results of bench-scale flotation demonstrate that the dosage of SPA can be reduced by about 80%,and that a better flotation index can be obtained using the proposed reagent system.The results of adsorption amount and contact angle measurements indicate that the rutile surface adsorbed not only a large amount of residual NaOl but also SPA and a small amount of NaOl remained on the amphibole surface in strong acidic solution.The hydrophobic difference between rutile and amphibole surfaces was therefore amplified in cleaning,and their further separation became much easier consequently.
文摘The separation of rutile from apatite by flotation and the mechanism of depressing the apatite of sodium hexametaphosphate were studied. The results showed that rutile and apatite could be separated by using alkyl-imino-bismethylene phosphoric acid and sodium hexametaphosphate as a collector and a regulator, respectively. Sodium hexametaphosphate could selectively dissolve calcium ions on the apatite surface, and make calcium ions break away from lattice binding through combining.
基金supported by the Institute of Science and High Technology and Environmental Sciences(No.1/1859)
文摘TiO2 nanowire arrays were successfully fabricated by liquid-phase deposition method using porous alumina templates. The obtained TiO2 nanowires were characterized using Raman spectroscopy, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, field emission scanning electron microscopy （FE- SEM）, transmission electron microscopy （TEM）, and selected area electron diffraction （SAED） analysis. Results of electron microscopic observations indicated that the nanowires were smooth and uniform with a diameter of about 50-80 nm and several micrometers in length. SAED, Raman, and XRD mea- surements showed that TiO2 nanowires were single-crystalline with a pure rutile structure after heating at 800 ~C for 10 h. In this situation, the nanowire constituents grew preferentially along the 〈001〉 direction. Furthermore, the formation process and mechanistic study of the Ti02 nanowire arrays were proposed and discussed in detail. The nanowires are clearly produced by the deposition of TiO2 particles on the inner wall of the template nanochannels.
基金supported by the National Natural Science Foundation of China(No.20977086,21076196,21177115)the Science and Technology Project of Zhejiang Province,China(No.2012C23026,2011C31041)
文摘A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a futile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80：20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.
文摘We report the discovery of TiO_(2)-Ⅱ in the unmelted rock of the shocked Suizhou L6 chondrite.Natural TiO_(2)-Ⅱ was previously found in ultrahigh-pressure metamorphic and mantle-derived rocks,terrestrial impact structures,and tektite.Our microscopic,Raman spectroscopic,electron microprobe and transmission electron microscopic investigations have revealed:(1) All observed TiO_(2)-Ⅱ grains are related with ilmenite and pyrophanite;(2) TiO_(2)-Ⅱ occurs as needle-and leaf-shaped inclusions in llmenite and patch-,tape-shaped body in pyrophanite;(3)The composition of TiO_(2)-Ⅱ is identical with that of its precursor rutile;(4) The Raman spectrum of TiO_(2)-Ⅱ is in good agreement with that of natural and synthesized α-PbO_(2)-type TiO_(2);(5) TiO_(2)-Ⅱ occurs mainly in the form of well-ordered nano-domains and small mis-orientation among the domains can be observed.(6) All electron diffraction reflections from TiO_(2)-Ⅱ can be indexed to α-PbO_(2)structure in space group Pbcn with lattice parameters of a=4.481 ?,b=5.578 A and c=4.921 A;(7) The exsolution inclusions of rutile from host ilmenite are mostly connected with an alternation process along the lamellar twinning plane of ilmenite induced by shockinduced high pressure and high temperature;(8) The P-T regime of 20-25 GPa and 1000 ℃ estimated for the Suizhou unmelted rock is suitable for phase transition of rutile into TiO_(2)-Ⅱ phase.
