Chin Kui Cheng

Schottky barrier and surface plasmonic resonance phenomena towards the photocatalytic reaction: study of their mechanisms to enhance photocatalytic activity

Metals are doped on semiconductors to enhance the activity of photocatalysts and two possible phenomena can happen at the interfaces of the semiconductors: Schottky barrier formation and Surface Plasmonic Resonance (SPR). Schottky barriers can improve the photoactivity of a reaction by trapping and prolonging the life of the electron. While SPR has the ability to create an electromagnetic field which can improve the photoreaction in three ways: photon scattering, Plasmon Resonance Energy Transfer (PRET) and hot electron excitation. Although both phenomena have been well grounded throughout the field, one crucial ambiguity is still found based on the proposed mechanisms, specifically, what is the direction of electron flow – from metal to semiconductor or vice versa? This feature article reviews the mechanism focusing on how Schottky barrier and SPR phenomena help to improve a photoreaction, as well as the paradox between the Schottky barrier and SPR in the matter of the direction of electron flow in the metal/semiconductor system.

Characterization of La-promoted Ni/Al2O3 catalysts for hydrogen production from glycerol dry reforming

In the current paper, dry (CO2)-reforming of glycerol, a new reforming route, was carried out over alumina (Al2O3)-supported, non-promoted and lanthanum-promoted nickel (Ni) catalysts. Both sets of catalysts were synthesized via a wet co-impregnation procedure. Physicochemical characterization of the catalysts showed that the promoted catalyst possessed smaller metal crystallite size, hence higher metal dispersion compared to the virgin Ni/Al2O3 catalyst. This was also corroborated by the surface images captured by the FESEM analysis. From temperature-programmed calcination analysis, the derivative weight profiles revealed two peaks, which represent a water elimination peak at a temperature range of 373 to 473 K followed by nickel nitrate decomposition from 473 to 573 K. In addition, BET surface area measurements gave 85.0 m2·g−1 for the non-promoted Ni catalyst, whilst the promoted catalysts showed an average of 1% to 6% improvement depending on the La loadings. Significantly, reaction studies at 873 K showed that glycerol dry reforming successfully produced H2. The 2%La-Ni/Al2O3 catalyst, which possessed the largest BET surface area, gave an optimum H2 generation (9.70%) at a glycerol conversion of 24.5%.

Synthesis and characterization of a CaFe2O4 catalyst for oleic acid esterification

Esterification of free fatty acid (oleic acid) with ethanol over a calcium ferrite catalyst was investigated in the present study. The calcium ferrite catalyst (CaFe2O4) was synthesized by the sol–gel method, which exhibited high catalytic activity for esterification of oleic acid. The morphology and size (500–1000 nm) of the synthesized catalyst were observed by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) was used to ensure the absence of impurities. The orthorhombic structure of calcium ferrite was exposed by X-ray diffractometry (XRD). The effects of reaction variables such as catalyst loading, methanol to acid ratio, reaction time and temperature on the conversion of fatty acids were studied. The optimum conditions for the esterification process was a molar ratio of alcohol to oleic acid at 12 : 1 with 5 wt% of CaFe2O4 at 70 °C with a reaction time of 2 h. XRD patterns of the recycled catalyst evidenced that the catalyst structure was unchanged up to the 3rd cycle, which indicated the long life of the catalyst.

A novel photomineralization of POME over UV-responsive TiO2 photocatalyst: kinetics of POME degradation and gaseous product formations

Traditionally, palm oil mill effluent (POME) is treated via open ponding system, which however is land-intensive and requires long hydraulic retention time. For the first time, this paper reports, simultaneously, the kinetics of photocatalytic degradation of POME and the assessment of its gaseous product formations. Characterization of the as-received UV-responsive TiO2 showed that anatase was the predominant crystalline phase with an estimated crystallite size of 45.7 nm and band gap energy of 3.15 eV based on the UV-vis DRS scanning. Moreover, N2-physisorption revealed that the BET specific surface area for TiO2 was 8.73 m2 g−1 with pore size of 22.4 nm. When the photoreactor was blanketed with N2 gas only at a TiO2 loading of 0.5 g L−1, POME degradation was only 4%. Significantly, in the presence of O2, the degradation of POME achieved 23%, and can even attain a maximum of 52.0% at TiO2 loading of 1.0 g L−1 after 240 min of UV-irradiation. This has demonstrated that the hydroxyl generation rate from water species (prevalent in N2-blanket) was considerably slower compared to the hydroxyl generation from the superoxide pathway that originates from externally-supplied O2. It was also found that the POME degradation kinetics adhered to the 1st-order reaction with specific reaction rates (k) ranging from 0.70 × 10−3 to 2.90 × 10−3 min−1. Interestingly, our assessment of the gaseous product formations revealed that the photoreaction employing 1.0 g L−1 TiO2 produced the highest amount of CO2 (38 913 μmol) while 0.5 g L−1 TiO2 produced the highest amount of CH4 (361 μmol). From the FTIR scanning of used catalyst, we can confirm that the chemisorption of organics was practically absent. This has led us to believe that the primary role of TiO2 was to generate hydroxyls for direct attack on the organic compounds in the POME and eventually decompose them into simpler intermediates, CH4, CO2, and water. Moreover, after 20 h under the UV irradiation, POME degradation attained 78.0% and the final COD level dropped to 37 ppm, which is safe to be discharged.

CO2 reforming of glycerol over La-Ni/Al2O3 catalyst: A longevity evaluative study

This paper reports on the longevity of glycerol-dry (CO2) reforming over the lanthanum (La) promoted Ni/Al2O3 catalysts. The XRD results showed that the Ni particle was well-dispersed in the presence of La promoter. In addition, via the NH3-TPD analysis, it was found that the La promoter has reduced the acidity of Ni catalyst which may have explained the mitigation of carbon laydown. It was determined that the 3.0 wt% La-promoted Ni/Al2O3 catalyst possessed the largest BET specific surface area of 97 m2·g−1. Consequently, it yielded the best catalytic longevity performance with conversion attained more than 90%, even after 72 h of reaction duration. Significantly, it can be confirmed that the presence of CO2 during the glycerol dry reforming was essential in reducing carbon deposition, most likely via gasification pathway. This has ensured a stability of catalytic activity for a long reaction period (72 h).

Catalytic Performance of Cement Clinker Supported Nickel Catalyst in Glycerol Dry Reforming

The paper reports the development of cement clinker-supported nickel (with metal loadings of 5 wt%, 10 wt%, 15 wt% and 20 wt%) catalysts for glycerol dry (CO2) reforming reaction. XRF results showed that CaO constituted 62.0% of cement clinker. The physicochemical characterization of the catalysts revealed 32-folds increment of BET surface area (SBET) with the addition of nickel metal into the cement clinker, which was also corroborated by FESEM images. Significantly, XRD results suggested different types of Ni oxides formation with Ni loading, whilst Ca3SiO5 and Ca2Al0.67Mn0.33FeO5 were the main crystallite species for pure cement clinker. Temperature-programmed reduction analysis yielded three domains of H2 reduction peaks, viz. centered at approximately 750 K referred to as type-I peaks, another peaks at 820 K denoted as type-II peaks and the highest reduction peaks, type-III recorded at above 1000 K. 20 wt% Ni was found to be the best loading with the highest XG and H2 yield, whilst the lowest methanation activity. Syngas with lower H2/CO ratios (0.6 to 1.5) were readily produced from glycerol dry reforming at CO2-to-Glycerol feed ratio (COR) of unity. Nonetheless, carbon deposit comprised of whisker type (Cv) and graphitic-like type (Cc) species were found to be in majority on 20 wt%Ni/CC catalysts.

Process Modelling, Thermodynamic Analysis and Optimization of Dry Reforming, Partial Oxidation and Auto-Thermal Methane Reforming for Hydrogen and Syngas Production

Abstract In this work, process modelling, thermodynamic analysis and optimization of stand-alone dry and partial oxidation reforming of methane as well as, the auto-thermal reforming processes were investigated. Firstly, flowsheet models were developed for both the stand-alone systems and auto-thermal reforming process using ASPEN HYSYS®. Furthermore, thermodynamic studies were conducted for the stand-alone and auto-thermal reforming processes for temperatures range of 200–1000°C and pressure range of 1–3 bar using Gibbs free energy minimization methods which was also performed using ASPEN HYSYS®. The simulation of the auto-thermal reforming process was also performed at 20 bar to mimic industrial process. Process parameters were optimized in the combined reforming process for hydrogen production using desirability function. The simulation results show that 84.60 kg/h, 62.08 kg/h and 154.7 kg/h of syngas were produced from 144 kg/h, 113 kg/h and 211 kg/h of the gas fed into the Gibbs reactor at CH4/CO2/O2 ratio 1:1:1 for the stand-alone dry reforming, partial oxidation reforming and auto-thermal processes respectively. Equilibrium conversion of CH4, CO2, O2 were thermodynamically favoured between 400 and 800°C with highest conversions of 100%, 95.9% and 86.7% for O2, CO2 and CH4 respectively. Highest yield of 99% for H2 and 40% for CO at 800°C was obtained. The optimum conditions for hydrogen production were obtained at CH4/CO2, CH4/O2 ratios of 0.634, 0.454 and temperature of 800°C respectively. The results obtained in this study corroborate experimental studies conducted on auto-thermal reforming of methane for hydrogen and syngas production.

Pyrolysis production of fruit peel biochar for potential use in treatment of palm oil mill effluent

Fruit peel, an abundant waste, represents a potential bio-resource to be converted into useful materials instead of being dumped in landfill sites. Palm oil mill effluent (POME) is a harmful waste that should also be treated before it can safely be released to the environment. In this study, pyrolysis of banana and orange peels was performed under different temperatures to produce biochar that was then examined as adsorbent in POME treatment. The pyrolysis generated 30.7-47.7 wt% yield of a dark biochar over a temperature ranging between 400 and 500 °C. The biochar contained no sulphur and possessed a hard texture, low volatile content (≤34 wt%), and high amounts of fixed carbon (≥72 wt%), showing durability in terms of high resistance to chemical reactions such as oxidation. The biochar showed a surface area of 105 m2/g and a porous structure containing mesopores, indicating its potential to provide many adsorption sites for use as an adsorbent. The use of the biochar as adsorbent to treat the POME showed a removal efficiency of up to 57% in reducing the concentration of biochemical oxygen demand (BOD), chemical oxygen demand COD, total suspended solid (TSS) and oil and grease (O&G) of POME to an acceptable level below the discharge standard. Our results indicate that pyrolysis shows promise as a technique to transform banana and orange peel into value-added biochar for use as adsorbent to treat POME. The recovery of biochar from fruit waste also shows advantage over traditional landfill approaches in disposing this waste.

Microwave pyrolysis with KOH/NaOH mixture activation: A new approach to produce micro-mesoporous activated carbon for textile dye adsorption

A micro-mesoporous activated carbon (AC) was produced via an innovative approach combining microwave pyrolysis and chemical activation using NaOH/KOH mixture. The pyrolysis was examined over different chemical impregnation ratio, microwave power, microwave irradiation time and types of activating agents for the yield, chemical composition, and porous characteristic of the AC obtained. The AC was then tested for its feasibility as textile dye adsorbent. About 29 wt% yield of AC was obtained from the banana peel with low ash and moisture (<5 wt%), and showed a micro-mesoporous structure with high BET surface area (≤1038 m2/g) and pore volume (≤0.80 cm3/g), indicating that it can be utilized as adsorbent to remove dye. Up to 90% adsorption of malachite green dye was achieved by the AC. Our results indicate that the microwave-activation approach represents a promising attempt to produce good quality AC for dye adsorption.

Optimization of photocatalytic degradation of palm oil mill effluent in UV/ZnO system based on response surface methodology

This paper reports on the optimization of palm oil mill effluent (POME) degradation in a UV-activated-ZnO system based on central composite design (CCD) in response surface methodology (RSM). Three potential factors, viz. O2 flowrate (A), ZnO loading (B) and initial concentration of POME (C) were evaluated for the significance analysis using a 23 full factorial design before the optimization process. It is found that all the three main factors were significant, with contributions of 58.27% (A), 15.96% (B) and 13.85% (C), respectively, to the POME degradation. In addition, the interactions between the factors AB, AC and BC also have contributed 4.02%, 3.12% and 1.01% to the POME degradation. Subsequently, all the three factors were subjected to statistical central composite design (CCD) analysis. Quadratic models were developed and rigorously checked. A 3D-response surface was subsequently generated. Two successive validation experiments were carried out and the degradation achieved were 55.25 and 55.33%, contrasted with 52.45% for predicted degradation value.