In this study, Ni nanoparticle supported by graphene oxide (GO) (Ni-GO) is successfully synthesized through hydrothermal synthesis and calcination, and Cr(VI) is extracted from aqueous solution. The morphology and structure of Ni- GO composites are characterized by scanning electron microscopy (SEM), trans mission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). High-resolution transmission electron microscopy (HRTEM) and XRD confirms the high dispersion of Ni nanoparticle after support by GO. Loading Ni on GO can obviously enhance the stability of Ni-GO composites. It can be calculated from TGA that the mass percentage of Ni is about 60.67%. The effects of initial pH and reaction time on Cr(VI) removal ability of Ni-GO are investigated. The results indicate that the removal efficiency of Cr(VI) is greater than that of bared GO. Ni-GO shows fast removal capacity for Cr(VI) (<25 min) with high removal efficiency. Dynamic experiments show that the removal process conforms to the quasi-second order model of adsorption, which indicates that the rate control step of the removal process is chemical adsorption. The removal capacity increases with the increase of temperature, indicating that the reaction of Cr(VI) on Ni-GO composites is endothermic and spontaneous. Combined with tests and characterization, the mechanism of Cr(VI) removal by rapidly adsorption on the surface of Ni-GO and reduction by Ni nanoparticle is investigated. The above results show that Ni-GO can be used as a potential remediation agent for Cr(VI)-contaminated groundwater.

Nitrogen-doped carbon nanosheets with a developed porous structure were prepared from polyurethane foams by hydrothermal carbonization following ZnCl2 chemical activation. Scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, solid state 13C nuclear magnetic resonance (NMR) spectra and X-ray photoelectron spectroscopy were used to characterize the nitrogen-doped carbon nanosheet structure and composition. The removal of Cr(VI) by the N-doped carbon nanosheets was investigated. The results showed that the maximum removal capacity for chromium of 188 mg/g was found at pH=2.0 with PHC-Z-3. pH had an important effect on Cr(VI) removal and the optimal pH was 2.0. Moreover, amino groups and carboxyl groups in the nitrogen-doped carbon nanosheet played important roles in Cr(VI) removal, and promoted the reduction of Cr(VI) to Cr(III).

In this study, a flat-type photocatalytic reactor is applied under solar irradiation for simultaneous treatment of target pollutants: reduction of Cr(VI) to Cr(III) and oxidation of EDCs (BPA, EE2, E2). An immobilized type of photocatalyst was fabricated to have self-grown nanotubes on its surface in order to overcome limitations of powdery photocatalyst. Moreover, Ti mesh form was chosen as substrate and modified to have both larger surface area and photocatalyst content. Ti mesh was anodized at 50V and 25°C for 30min in the mixed electrolytes (NH4F-H2O-C2H6O2) and annealed at 450°C for 2 hours in ambient oxygen to have anatase structure. Surface characterization was done with SEM and XRD methodologies. Fabricated NTT was applied to water treatment, and coexisting Cr(VI) and organics (EDCs) enhanced each other's reactions by scavenging holes and electrons and thus impeding recombination. Also, several experiments were conducted outdoor under direct sunlight and it was observed that both solar-tracking and applying modified photocatalyst were proven to enhance reaction efficiency.

In this study, flat-type photocatalytic reaction system is applied to reduce toxic hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)) in aqueous solution under UV irradiation. To overcome the limitation of conventional photocatalysis, a novel approach toward photocatalytic system for reduction of hexavalent chromium including nanotubular TiO2 (NTT) on two kinds of titanium substrates (foil and mesh) were established. In addition, modified Ti substrates were prepared by bending treatment to increase reaction efficiency of Cr(VI) in the flat-type photocatalytic reactor. For the fabrication of NTT on Ti substrates, Ti foil and mesh was anodized with mixed electrolytes (NH4F-H2O-C2H6O2) and then annealed in ambient oxygen. The prepared NTT arrays were uniformly grown on two Ti substrates and surface property measurements were performed through SEM and XRD. Hydraulic retention time(HRT) and substrate type were significantly affected the Cr(VI) reduction. Hence, the photocatalytic Cr(VI) reduction was observed to be highest up to 95% at bended(modified) Ti mesh and lowest HRT. Especially, Ti mesh was more effective as NTT substrate in this research.

The adsorption and reduction of Cr (VI) to Cr (III) by surface modified activated carbon (AC) in an aqueous solution was studied. The effects of surface modifications on the properties of the carbons were investigated by the analysis of specific surface area, carbon surface pH, acid/base surface values and functional groups. In order to understand the Cr(VI) adsorption and reduction ratio from Cr(VI) to Cr(III), the Cr adsorption capacity of AC was also measured and discussed by using inductively coupled plasma and UV spectrophotometer. The modifications bring about substantial variation in the chemical properties whereas the physical properties such as specific surface area, pore volume and pore size distribution nearly were not changed. Total Cr adsorption efficiency of as-received activated carbon (R-AC) and nitric acid treated activated carbon (N1-AC and N2-AC) were recorded on 98.2, 99.7 and 100%. Cr(III) reduction efficiency of R-AC increased largely from 0.4% to 28.3% compared to N1-AC and N2-AC.

A carbonaceous sorbent was prepared from rice husk via sulphuric acid treatment. After preparation and washing, the wet carbon with moisture content 85% was used in its wet status in this study due to its higher reactivity towards Cr(VI) than the dry carbon. The interaction of Cr(VI) and the carbon was studied and two processes were investigated in terms of kinetics and equilibrium namely Cr(VI) removal and chromium sorption. Cr(VI) removal and chromium sorption were studied at various initial pH (1.6-7), for initial Cr(VI) concentration (100 mg/l). At equilibrium, maximum Cr(VI) removal occurred at low initial pH (1.6-2) where, Cr(III) was the only available chromium species in solution. Cr(VI) removal, at such low pH, was related to the reduction to Cr(III). Maximum chromium sorption (60.5 mg/g) occurred at initial pH 2.8 and a rise in the final pH was recorded for all initial pH studied. For the kinetic experiments, approximate equilibrium was reached in 60-100 hr. Cr(VI) removal data, at initial pH 1.6-2.4, fit well pseudo first order model but did not fit pseudo second order model. At initial pH 2.6-7, Cr(VI) removal data did not fit, anymore, pseudo first order model, but fit well pseudo second order model instead. The change in the order of Cr(VI) removal process takes place in the pH range 2.4-2.6 under the experimental conditions. Other two models were tested for the kinetics of chromium sorption with the data fitting well pseudo second order model in the whole range of pH. An increase in cation exchange capacity, sorbent acidity and base neutralization capacity was recorded for the carbon sorbent after the interaction with acidified Cr(VI) indicating the oxidation processes on the carbon surface accompanying Cr(VI) reduction.

This paper has applied a simple model to the mass transfer mechanism of Cr(VI) with crownether in a batch-type, supported liquid membrane module. Concentration at pH 3 are as follows : 0.012 kmol/m3≤18-crown-6≤0.036 kmol/m3 and 20 g/m3≤ Cr(VI)≤500 g/m3. The measured values of forward- and backward-reaction rate constants between Cr(VI) and 18-crown-6 were used to simulate the model with the mass conservation equation and associated boundary conditions. Comparison between the experimental and simulated facilitated factor of Cr(VI) transport led to classification of reaction regions.

The effect of temperature on the removal process of Cr(VI) ion contained in wastewater by a precipitation method has been investigated for the improvement of its design and operation. The distribution diagram of chromium ion was constructed by employing the MINTEQ program and the quantitative feature of Cr(VI) depending on pH was investigated. As the temperature increases, the relative amount of H2CrO4 was examined to be raised and the pH range in which H2CrO4 exists as a stable form was also investigated to be extended according to the temperature. Cr(VI) ion was shown to be changed from HCrO4 − to Cr2O7 2− as the concentration of Cr(VI) ion is increased in the neutral pH condition and the concentration of Cr(VI) ion which is necessary for the ionic transformation was observed to rise in the acidic and alkaline conditions. The major reactant which involved in the reduction reaction for the removal of Cr(VI) ion was examined to be HCrO4 − and the reduction of Cr(VI) ion to Cr(III) ion was investigated to be influenced much by the temperature change at higher pH conditions. The reduction reaction of Cr(VI) ion for its removal as a precipitate was examined to be promoted as the temperature decreases and pH is lowered. In addition, the stable region of Cr(OH)3 was shown to be enlarged with temperature based on the thermodynamic estimation and it was thought to be necessary to design and control the precipitating process of Cr(VI) ion by considering the thermal characteristics of reduction and precipitation stage.

유기탄소와 Cr(VI)와의 반응을 연구하여 위하여 컬럼 실험을 실시하였다. 컬럼 실험은 거름토의 유기탄소와 수용액 속의 Cr(VI)와의 반응 후 시간별로 채취한 컬럼의 유출수와 반응 후 컬럼에 남은 고체물질에 대하여 화학분석과 SEM 관찰을 실시하였다. 컬럼에 공급된 Cr(VI)은 초기 유출수에서는 검출되지 않다가 약 8 PV (pore volume) 후 급격한 농도 증가를 보이며 공급수의 농도(20 mg/kg)까지 높아져 본 실험 조건에서 초기에 유기탄소와 Cr(VI)과의 반응에 의하여 일정 기간 동안 제거됨을 보인다. 전반적으로 유출수에서 측정된 양이온과 음이온의 농도는 PO4를 제외하고 초기에 증가하였다가 시간이 지나면서 감소하는 경향을 보인다. 대부분의 이온들이 공급수에는 검출되진 않았거나 매우 낮은 농도임을 감안하면 이 이온들은 주로 유기탄소에서 유출된 것으로 판단된다. SEM 관찰결과 Cr은 유기탄소 표면에 Fe와 함께 공침되었음을 보이고 일부 침전물에 Mn, Ni, Co 등과 같은 금속들이 함께 함유되어있음을 보여준다. 이는 유기탄소 표면의 환원환경에서 Cr(VI)가 환원이 되어 Cr(OH)3로 침전되면서 Fe(OH)3와 같이 공침하였음을 보여주며 Fe의 존재가 Cr의 침전에 있어서 매우 중요함을 지시한다. 추후 용해성 Fe와 Mn과 같은 원소들이 더 이상 용출되지 않으면 Cr(VI)는 더 이상 침전 반응으로 제거되지 않는다. 다른 이온들과 달리 PO4의 경우 초기 유출수에서 감소를 보이고 추후에 농도가 증가하는데 이는 유기탄소에 포함되어 있던 PO4가 유출된 후에 Cr과 Fe의 침전물에 효과적으로 흡착이 되고 침전물이 더 이상 생성되지 않게 되면 원래 유기탄소로부터 용해되어 나온 PO4의 농도로 회귀되어 일정한 값을 보이는 것으로 생각된다.