Graphene is one of the most promising materials in the field of nanotechnology and has attracted a tremendous amount of research interest in recent years. Due to its large specific surface area, high thermal conductivity, and superior electron mobility, graphene is regarded as an extremely attractive component for the preparation of composite materials. At the same time, the use of photocatalysts, particularly TiO(2), has also been widely studied for their potential in addressing various energy and environmental-related issues. However, bare TiO(2) suffers from low efficiency and a narrow light-response range. Therefore, the combination of graphene and TiO(2) is currently one of the most active interdisciplinary research areas and demonstrations of photocatalytic enhancement are abundant. This Review presents and discusses the current development of graphene-based TiO(2) photocatalysts. The theoretical framework of the composite, the synthetic strategies for the preparation and modification of graphene-based TiO(2) photocatalysts, and applications of the composite are reviewed, with particular attention on the photodegradation of pollutants and photocatalytic water splitting for hydrogen generation.
As an indispensable energy source, ammonia plays an essential role in agriculture and various industries. Given that the current ammonia production is still dominated by the energy-intensive and high carbon footprint Haber-Bosch process, photocatalytic nitrogen fixation represents a low-energy consuming and sustainable approach to generate ammonia. Heterostructured photocatalysts are hybrid materials composed of semiconductor materials containing interfaces that make full use of the unique superiorities of the constituents and synergistic effects between them. These promising photocatalysts have superior performances and substantial potential in photocatalytic reduction of nitrogen. In this review, a wide spectrum of recently developed heterostructured photocatalysts for nitrogen fixation to ammonia are evaluated. The fundamentals of solar-to-ammonia conversion, basic principles of various heterojunction photocatalysts and modification strategies are systematically reviewed. Finally, a brief summary and perspectives on the ongoing challenges and directions for future development of nitrogen photofixation catalysts are also provided.
The utilization of carbon dioxide for the production of valuable chemicals via catalysts is one of the efficient ways to mitigate the greenhouse gases in the atmosphere. It is known that the carbon dioxide conversion and product yields are still low even if the reaction is operated at high pressure and temperature. The carbon dioxide utilization and conversion provides many challenges in exploring new concepts and opportunities for development of unique catalysts for the purpose of activating the carbon dioxide molecules. In this paper, the role of carbon-based nanocatalysts in the hydrogenation of carbon dioxide and direct synthesis of dimethyl carbonate from carbon dioxide and methanol are reviewed. The current catalytic results obtained with different carbon-based nanocatalysts systems are presented and how these materials contribute to the carbon dioxide conversion is explained. In addition, different strategies and preparation methods of nanometallic catalysts on various carbon supports are described to optimize the dispersion of metal nanoparticles and catalytic activity.
In this work, heterogeneous photocatalysis was used to treat pulp and paper mill effluent (PPME). Magnetically retrievable Fe2O3-TiO2 was fabricated by employing a solvent-free mechanochemical process under ambient conditions. Findings elucidated the successful incorporation of Fe2O3 into the TiO2 lattice. Fe2O3-TiO2 was found to be an irregular and slightly agglomerated surface morphology. In comparison to commercial P25, Fe2O3-TiO2 exhibited higher ferromagnetism and better catalyst properties with improvements in surface area (58.40 m2/g), pore volume (0.29 cm3/g), pore size (18.52 nm), and band gap (2.95 eV). Besides, reusability study revealed that Fe2O3-TiO2 was chemically stable and could be reused successively (five cycles) without significant changes in its photoactivity and intrinsic properties. Additionally, this study demonstrated the potential recovery of Fe2O3-TiO2 from an aqueous suspension by using an applied magnetic field or sedimentation. Interactive effects of photocatalytic conditions (initial effluent pH, Fe2O3-TiO2 dosage, and air flow-rate), reaction mechanism, and the presence of chemical oxidants (H2O2, BrO3-, and HOCl) during the treatment process of PPME were also investigated. Under optimal conditions (initial effluent pH = 3.88, [Fe2O3-TiO2] = 1.3 g/L, and air flow-rate = 2.28 L/min), the treatment efficiency of Fe2O3-TiO2 was 98.5% higher than the P25. Based on Langmuir-Hinshelwood kinetic model, apparent rate constants of Fe2O3-TiO2 and P25 were 9.2 × 10-3 and 2.7 × 10-3 min-1, respectively. The present study revealed not only the potential of using magnetic Fe2O3-TiO2 in PPME treatment but also demonstrated high reusability and easy separation of Fe2O3-TiO2 from the wastewater.
In this paper, noble-metal Pt nanoparticles of around 2.5 nm were deposited on graphitic carbon nitride (g-C3N4) synthesized by a chemical reduction process in ethylene glycol. Compared with pure g-C3N4, the resulting Pt-loaded g-C3N4 (Pt/CN) exhibited a considerable improvement in the photoreduction of CO2 to CH4 in the presence of water vapor at ambient temperature and atmospheric pressure under visible light irradiation. 2 wt% Pt-loaded g-C3N4 (2Pt/CN) nanocomposites produced the highest CH4 yield of 13.02 μmol gcatalyst(-1) after 10 h of light irradiation, which was a 5.1-fold enhancement in comparison with pure g-C3N4 (2.55 μmol gcatalyst(-1)). The remarkable photocatalytic activity of Pt/CN nanostructures in the CH4 production was ascribed to the enhanced visible light absorption and efficient interfacial transfer of photogenerated electrons from g-C3N4 to Pt due to the lower Fermi level of Pt in the Pt/CN hybrid heterojunctions as evidenced by the UV-Vis and photoluminescence studies. The enriched electron density on Pt favored the reduction of CO2 to CH4via a multi-electron transfer process. This resulted in the inhibition of electron-hole pair recombination for effective spatial charge separation, thus enhancing the photocatalytic reactions. Based on the experimental results obtained, a plausible mechanism for improved photocatalytic performance associated with Pt/CN was proposed.
A facile one-pot impregnation-thermal reduction strategy was employed to fabricate sandwich-like graphene-g-C3N4 (GCN) nanocomposites using urea and graphene oxide as precursors. The GCN sample exhibited a slight red shift of the absorption band edge attributed to the formation of a C-O-C bond as a covalent cross linker between graphene and g-C3N4. The GCN sample demonstrated high visible-light photoactivity towards CO2 reduction under ambient conditions, exhibiting a 2.3-fold enhancement over pure g-C3N4. This was ascribed to the inhibition of electron-hole pair recombination by graphene, which increased the charge transfer.
A facile and dopant-free strategy was employed to fabricate oxygen-rich TiO2 (O2-TiO2) with enhanced visible light photoactivity. Such properties were achieved by the in situ generation of oxygen through the thermal decomposition of the peroxo-titania complex. The O2-TiO2 photocatalyst exhibited high photoactivity towards CO2 reduction under visible light.
Photocatalytic reduction of carbon dioxide (CO2) into hydrocarbon fuels such as methane is an attractive strategy for simultaneously harvesting solar energy and capturing this major greenhouse gas. Incessant research interest has been devoted to preparing graphene-based semiconductor nanocomposites as photocatalysts for a variety of applications. In this work, reduced graphene oxide (rGO)-TiO2 hybrid nanocrystals were fabricated through a novel and simple solvothermal synthetic route. Anatase TiO2 particles with an average diameter of 12 nm were uniformly dispersed on the rGO sheet. Slow hydrolysis reaction was successfully attained through the use of ethylene glycol and acetic acid mixed solvents coupled with an additional cooling step. The prepared rGO-TiO2 nanocomposites exhibited superior photocatalytic activity (0.135 μmol gcat-1 h-1) in the reduction of CO2 over graphite oxide and pure anatase. The intimate contact between TiO2 and rGO was proposed to accelerate the transfer of photogenerated electrons on TiO2 to rGO, leading to an effective charge anti-recombination and thus enhancing the photocatalytic activity. Furthermore, our photocatalysts were found to be active even under the irradiation of low-power energy-saving light bulbs, which renders the entire process economically and practically feasible.
Lymphoma is a relatively common group of neoplasms diagnosed in hospital practice. This study aims to elucidate the pattern of this disease encountered in a public service hospital of the Ministry of Health, Malaysia.
Lymph node excision biopsy is commonly carried out for the investigation of lymphadenopathy. The objective of this study is to elucidate the pattern of nodal pathology seen in a private pathology practice. A total of 137 nodal biopsies for primary investigation of nodal enlargement were retrieved from the files in a private diagnostic pathology laboratory in the year 1997. Lymph nodes excised for cancer staging were excluded from this study. The histology was reviewed based on H&E stained sections, and with additional histochemical and immunoperoxidase stains when deemed necessary. Cases of malignant lymphomas were sub-classified with the aid of further immunophenotyping using a panel of monoclonal and polyclonal lymphoid antibodies. One case was excluded from this study due to inadequate tissue for further assessment. There were 58 males and 78 females, giving a ratio of 1:1.3 in the remaining 136 cases. They consisted of 13 Malays (M), 108 Chinese (C), 14 Indians (I) and 1 other ethnic group (O). The ratio of M:C:I:O was 1:8.3:1.1:0.1. The majority of the cases were in the age range of 20 to 50 years. The pathology consisted of 17 (12.5%) malignant lymphomas [6 Hodgkin's lymphoma, 11 non-Hodgkin's lymphoma], 35 (25.7%) metastatic carcinomas, 45 (33.1%) reactive hyperplasia, 19 (13.9%) tuberculosis, 11 (8.2%) Kikuchi's disease and 9 (6.6%) others (Castleman's disease 2, cat scratch disease 2, Kimura's disease 1, sarcoidosis 1, non-specific lymphadenitis 3). All categories of nodal disease showed approximately similar ratio of ethnic and gender distribution as above, except for Kikuchi's disease, for which 100% of the patients were female. The most common site of biopsy was from the head and neck region, particularly the cervical group of nodes. The most common nodal pathology seen in the private laboratory was reactive hyperplasia, followed by metastatic carcinoma. Malignant lymphoma constituted only 12.5% of the cases.
Alginate microcapsules containing epoxy resin were developed through electrospraying method and embedded into epoxy matrix to produce a capsule-based self-healing composite system. These formaldehyde free alginate/epoxy microcapsules were characterized via light microscope, field emission scanning electron microscope, fourier transform infrared spectroscopy and thermogravimetric analysis. Results showed that epoxy resin was successfully encapsulated within alginate matrix to form porous (multi-core) microcapsules with pore size ranged from 5-100 μm. The microcapsules had an average size of 320 ± 20 μm with decomposition temperature at 220 °C. The loading capacity of these capsules was estimated to be 79%. Under in situ healing test, impact specimens showed healing efficiency as high as 86% and the ability to heal up to 3 times due to the multi-core capsule structure and the high impact energy test that triggered the released of epoxy especially in the second and third healings. TDCB specimens showed one-time healing only with the highest healing efficiency of 76%. The single healing event was attributed by the constant crack propagation rate of TDCB fracture test. For the first time, a cost effective, environmentally benign and sustainable capsule-based self-healing system with multiple healing capabilities and high healing performance was developed.
Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are thoroughly examined, with additional insights related to the charge transfer events for each strategy of the modified-TiO2 composites. Finally, we offer a summary and some invigorating perspectives on the major challenges and new research directions for future exploitation in this emerging frontier, which we hope will advance us to rationally harness the outstanding structural and electronic properties of {001} facets for various environmental and energy-related applications.
Titanium dioxide (TiO2 ) is one of the most widely investigated metal oxides because of its extraordinary surface, electronic, and photocatalytic properties. However, the large band gap of TiO2 and the considerable recombination of photogenerated electron-hole pairs limit its photocatalytic efficiency. Therefore, research attention is being increasingly directed towards engineering the surface structure of TiO2 on the atomic level (namely morphological control of {001} facets on the micro- and nanoscale) to fine-tune its physicochemical properties; this could ultimately lead to the optimization of selectivity and reactivity. This Review encompasses the fundamental principles to enhance the photocatalytic activity by using highly reactive {001}-faceted TiO2 -based composites. The current progress of such composites, with particular emphasis on the photodegradation of pollutants and photocatalytic water splitting for hydrogen generation, is also discussed. The progresses made are thoroughly examined for achieving remarkable photocatalytic performances, with additional insights with regard to charge transfer. Finally, a summary and some perspectives on the challenges and new research directions for future exploitation in this emerging frontier are provided, which hopefully would allow for harnessing the outstanding structural and electronic properties of {001} facets for various energy- and environmental-related applications.
A high concentration of phosphorus in wastewater may lead to excessive algae growth and deoxygenation of the water. In this work, nanofiltration (NF) of phosphorus-rich solutions is studied in order to investigate its potential in removing and recycling phosphorus. Wastewater samples from a pulp and paper plant were first analyzed. Commercial membranes (DK5, MPF34, NF90, NF270, NF200) were characterized and tested in permeability and phosphorus removal experiments. NF90 membranes offer the highest rejection of phosphorus; a rejection of more than 70% phosphorus was achieved for a feed containing 2.5 g/L of phosphorus at a pH <2. Additionally, NF90, NF200 and NF270 membranes show higher permeability than DK5 and MPF34 membranes. The separation performance of NF90 is slightly affected by phosphorus concentration and pressure, which may be due to concentration polarization and fouling. By adjusting the pH to 2 or adding sulfuric acid, the separation performance of NF90 was improved in removing phosphorus. However, the presence of acetic acid significantly impairs the rejection of phosphorus.
The unique characteristic of fast water permeation in laminated graphene oxide (GO) sheets has facilitated the development of ultrathin and ultrafast nanofiltration membranes. Here we report the application of fast water permeation property of immersed GO deposition for enhancing the performance of a GO/water nanofluid charged two-phase closed thermosyphon (TPCT). By benchmarking its performance against a silver oxide/water nanofluid charged TPCT, the enhancement of evaporation strength is found to be essentially attributed to the fast water permeation property of GO deposition instead of the enhanced surface wettability of the deposited layer. The expansion of interlayer distance between the graphitic planes of GO deposited layer enables intercalation of bilayer water for fast water permeation. The capillary force attributed to the frictionless interaction between the atomically smooth, hydrophobic carbon structures and the well-ordered hydrogen bonds of water molecules is sufficiently strong to overcome the gravitational force. As a result, a thin water film is formed on the GO deposited layers, inducing filmwise evaporation which is more effective than its interfacial counterpart, appreciably enhanced the overall performance of TPCT. This study paves the way for a promising start of employing the fast water permeation property of GO in thermal applications.
Lymphoma is a highly heterogeneous group of malignant disease. This study aimed to elucidate the pattern of lymphoma in the East Malaysian patient population. 107 cases of confirmed lymphomas from East Malaysian biopsy material were retrieved from the files of the Department of Pathology, University of Malaya, in the 3-year period between 1981 to 1983. With the use of a panel of lymphoid antibodies, the disease was sub-classified using the Rye classification for Hodgkin's lymphoma (HL) and the REAL classification for non-Hodgkin's lymphoma (NHL). All of the cases were tested for the presence of the Epstein-Barr virus by EBER-ISH. There were 11 (10.3%) HL, 80 (74.7%) B-NHL and 16 (15%) T-NHL. The HL:NHL ratio was 1:9. The most common tumour in children was Burkitt's lymphoma 7/13 (53.8%). In the adult group, there were 72/94 (76.6%) B-NHL ¿diffuse large cell type 51 (of which 2 were CD30+), Burkitt's lymphoma 8, follicular lymphoma 5, low grade MALT 2, mantle cell type 1 and not otherwise specified due to poor morphology 5¿, 13/94 (13.8%) T-NHL and 9/94 (9.6%) HL. Of the 9 adult HL, the most common subtype was nodular sclerosis (6, 66.7%). The EBER positive rate in classical HL, T-NHL, BL and B-NHL were 33.3%, 56.3%, 60.0% and 3.1% respectively. In conclusion, the spectrum of lymphoma seen in East Malaysia was rather similar to West Malaysia except for the very low prevalence of peripheral T-cell lymphoma (PTCL) in Sarawak (3.3%).
Improving the stability of cuprous oxide (Cu2 O) is imperative to its practical applications in artificial photosynthesis. In this work, Cu2 O nanowires are encapsulated by metal-organic frameworks (MOFs) of Cu3 (BTC)2 (BTC=1,3,5-benzene tricarboxylate) using a surfactant-free method. Such MOFs not only suppress the water vapor-induced corrosion of Cu2 O but also facilitate charge separation and CO2 uptake, thus resulting in a nanocomposite representing 1.9 times improved activity and stability for selective photocatalytic CO2 reduction into CH4 under mild reaction conditions. Furthermore, direct transfer of photogenerated electrons from the conduction band of Cu2 O to the LUMO level of non-excited Cu3 (BTC)2 has been evidenced by time-resolved photoluminescence. This work proposes an effective strategy for CO2 conversion by a synergy of charge separation and CO2 adsorption, leading to the enhanced photocatalytic reaction when MOFs are integrated with metal oxide photocatalyst.
Owing to its superior properties and versatility, graphene has been proliferating the energy research scene in the past decade. In this contribution, nitrogen (N-) and boron (B-) doped reduced graphene oxide (rGO) variants were investigated as a sole photocatalyst for the green production of H2 and their properties with respect to photocatalysis were elucidated for the first time. N- and B-rGOs were facilely prepared via the pyrolysis of graphene oxide with urea and boron anhydride as their respective dopant source. The pyrolysis temperature was varied (600-800 °C for N-rGO and 800-1000 °C for B-rGO) in order to modify dopant loading percentage (%) which was found to be influential to photocatalytic activity. N-rGO600 (8.26 N at%) and B-rGO1000 (3.59 B at%), which holds the highest at% from each of their party, exhibited the highest H2 activity. Additionally, the effects of the nature of N and B bonding configuration in H2 photoactivity were also examined. This study demonstrates the importance of dopant atoms in graphene, rendering doping as an effective strategy to bolster photocatalytic activity for standalone graphene derivative photocatalysts.
In the present work, two-dimensional bismuth oxybromide (BiOBr) was synthesized and coupled with co-catalyst molybdenum disulphide (MoS2) via a simple hydrothermal process. The photoactivity of the resulting hybrid photocatalyst (MoS2/BiOBr) was evaluated under the irradiation of 15 W energy-saving light bulb at ambient condition using Reactive Black 5 (RB5) as model dye solution. The photo-degradation of RB5 by BiOBr loaded with 0.2 wt% MoS2 (MoBi-2) exhibited more than 1.4 and 5.0 folds of enhancement over pristine BiOBr and titanium dioxide (Degussa, P25), respectively. The increased photocatalytic performance was a result of an efficient migration of excited electrons from BiOBr to MoS2, prolonging the electron-hole pairs recombination rate. A possible charge transfer diagram of this hybrid composite photocatalyst, and the reaction mechanism for the photodegradation of RB5 were proposed.
The engineering of surface oxygen vacancies (OVs) in WO3 was primitively done using a facile solvothermal method. The photocatalytic activities of the as-prepared samples were studied by evaluating their performances in the photocatalytic OER. The best sample (W-3) yielded 57.6 μmol of O2 in 6 h under the illumination of simulated sunlight.