Singapore

Development of highly-efficient and cost-effective water treatment techniques is critical to tackle global water crisis and membrane processes are promising among state-of-the-art water treatment technologies. We recently developed a few novel carbon-based electro-active filter technologies that could not only physically adsorb, but also electrochemically oxidize various refractory chemical contaminants. The efficacy and efficiency towards organic compounds electrooxidation were examined by several commonly detected organic pollutants (e.g. antibiotic tetracycline, refractory dyes and phenols). The filter materials we are currently working on include graphene, carbon nanotubes and other conductive nanofibers. The energy consumption per volume for our electroc-active filters were calculated to be only &lt;0.1 kW·hr/m3, which is better than other recently developed electrochemical systems, as well as other advance oxidation processes for water purification. 
In this presentation, we will share some of our recent experimental results that exemplified the advantages of contaminants removal using filters constructed with various nanomaterials integrated with a novel electrochemical approach in a flow-through system. The overall findings demonstrate that this integrated strategy is attractive and useful for both waste water treatment and drinking water purification.

MATERIALS FOR HUMANITY (MH 21)

Engineering Functional Electro-Active Filter toward Environmental Remediation

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MH 21 is arranged around 6 themes that focus attention on pressing needs that should be addressed to enhance the well-being of communities and provide a forum for presenting breakthrough discoveries.

Development of highly-efficient and cost-effective water treatment techniques is critical to tackle global water crisis and membrane processes are promising among state-of-the-art water treatment technologies. We recently developed a few novel carbon-based electro-active filter technologies that could not only physically adsorb, but also electrochemically oxidize various refractory chemical contaminants. The efficacy and efficiency towards organic compounds electrooxidation were examined by several commonly detected organic pollutants (e.g. antibiotic tetracycline, refractory dyes and phenols). The filter materials we are currently working on include graphene, carbon nanotubes and other conductive nanofibers. The energy consumption per volume for our electroc-active filters were calculated to be only <0.1 kW·hr/m3, which is better than other recently developed electrochemical systems, as well as other advance oxidation processes for water purification. 
In this presentation, we will share some of our recent experimental results that exemplified the advantages of contaminants removal using filters constructed with various nanomaterials integrated with a novel electrochemical approach in a flow-through system. The overall findings demonstrate that this integrated strategy is attractive and useful for both waste water treatment and drinking water purification.

technical paper

This presentation will cover Cr(VI) and methyl orange dye (MO) removal from wastewater by adsorption on biochar-derived porous carbon adsorbents. The first work presents a strategy for modifying carbon surfaces by doping both N and P functional groups for enhanced Cr(VI) adsorption from aqueous solutions. This talk will focus on Layered double hydroxides (LDHs) decorated porous carbons for simultaneous Cr(VI) and MO removal. Layered double hydroxides (LDHs) are currently attracting intense research interests as pollutant removing adsorbents due to their low cost, non-toxic, structure amenability, and anion exchange capability. Herein, 3-dimensional flower-like Ni/Al LDH was prepared to decorate H3PO4 activated biomass-derived porous carbons (PAB) via a facile and green hydrothermal method. The as-synthesized nanocomposites (Ni/Al@PAB) displayed favorable removal performance towards both Cr(VI) and MO from aqueous solution due to the inherited excellent Cr(VI) removal ability from PAB and MO removal ability from Ni/Al LDH. In a single-component removal system, the maximum adsorption capacity of 271.5 and 412.8 mg/g for Cr(VI) and MO were achieved on Ni/Al@PAB, respectively. Remarkably, the removal capacity of Cr(VI) and MO both increased in the Cr(VI)single bond MO binary system due to the synergistic effect including, (i) additional adsorption sites of N-containing groups from MO, (ii) electrostatic interactions by the reduced Cr(III), and (iii) mutual thermal compensation in the binary system. This work paved the way for designing novel LDHs-decorated porous carbon adsorbents and revealed that the acicular Ni/Al LDH decorated PAB could be applied as an efficient and simultaneous adsorbent for coexisting toxic pollutants situations.

Simultaneous and efficient removal of Cr(VI) and methyl orange on layered double hydroxides decorated porous carbons

Energy and Materials Research to Find Solutions for the Dual Challenge

Membranes used in water reuse and pollution control applications are often exposed to feed solution species (e.g., proteins, polysaccharides, humic materials) that adsorb or otherwise accumulate during the filtration run, and thus can cause fouling. This has many consequences, including increased energy usage, a need for more frequent cleaning, and shortened membrane life. Here we examine novel and feed-specific hydrophilic coatings to mitigate the effects of fouling with the goal of reducing fouling resistance and energy consumption.
The coatings examined here are based on dopamine (DA), a biomimetic self-polymerizing hydrophilic material. They include DA, dopamine blended with 2-(dimethylamino)ethyl methacrylate (DAEMA) and DAEMA polymer (PDAEMA), and a novel coating using the dopamine analog norepinephrine.
The coatings containing DAEMA or PDAEMA offered anti-microbial activity, whereas the norepinephrine coatings provided very smooth hydrophilic surfaces that resisted fouling at low coating amounts, thus reducing coating resistance. These coatings were applied to commercially available 30 kDa poly(ether sulfone) membranes using a batch dip-coating method for a range of reaction times up to 3 h. 
Membranes were tested in bench-scale filtration tests using a dead-end system with mixing. Measurements included mass of permeate as a function of time, temperature, and solute concentration. From these we calculated solution flux, resistance, and energy consumption. Membranes were characterized using contact angle, atomic force microscopy (AFM), attenuated total reflectance Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The coatings enhanced anti-fouling properties against model foulants (BSA, SA, and SRNOM), and two treated municipal wastewaters. The modified membranes exhibited less energy consumption and lower fouling resistance as compared to as-received membranes.

Hydrophilic coatings for water reuse and pollution control applications

Different green technologies have been investigated in our research group in the last two decades to produce clean energy and more efficient thermal systems with the purpose to reduce the emissions of pollutants. Simulations, experiments and thermal analysis have been performed to develop and improve the efficiency of Parabolic Trough Collectors (PTC). In this type of collectors, solar radiation reflected in a parabolic surface is concentrated to heat a fluid that circulates in an absorber receiver. One of the strategies to enhance the heat transfer of the PTCs is the application of nanofluids as a working fluid. These nanofluids are produced by dispersing nanoparticles in a fluid base with the purpose to increase their thermal properties. Nanofluids with nanoparticles of Al2O3, TiO2 and graphene dispersed in water and oil have been developed and characterized by our group. These nanofluids have been experimentally tested in a PTC for real operating conditions. We have also developed a hybrid PTC with photovoltaic cells in the receiver with the objective to generate simultaneously thermal and electrical energy. The technical and economic feasibility of a plant of hybrid PTCs to satisfy part of the demand of heat and electrical energy of the industry and the building sector have been investigated for different applications, climates and economic scenarios. 
In order to reduce the energy consumption of the buildings, the application of phase change materials (PCM) in components of the envelope, such as the roof and the walls, has been studied. The purpose of these PCMs is to reduce the heat gains of the buildings and delay the maximum peak loads because the thermal energy that is transfer through the envelope of the building is used to melt the material of the PCM. Experimental and simulations results performed in different types of buildings and climates are discussed. 
Finally, it is presented a computational platform (http://www.tecsb.com) developed by our group that use satellite information of solar radiation and available roof surface of a metropolitan area to predict the solar potential for generation of electrical and thermal energy with different solar collectors technology and to estimate the reduction of energy consumption in the building due to the application of different passive technologies such as PCM, reflective paintings and insulator materials. The program has the capability to provide an estimation of the reduction of CO2 emissions due to the use of these renewable and green technologies instead of technologies that burn fossil fuels.


Applications of parabolic solar collectors, nanofluids and phase change materials to reduce pollutant emissions

Conventionally, mechanical-recycled plastics have been irreversibly deteriorated in mechanical properties due to chemical degradation accompanied by molecular chain breakage, and it has been said that they can be applied to almost one-time downgrade recycling. On the other hand, we have found that the main cause of this deterioration of mechanical properties is physical degradation due to structural deformation inside of the plastic, and it is possible to improve the mechanical properties by using self resilience ability of plastic. Furthermore, it has been clarified that the mechanical properties can be improved efficiently by using a newly designed extruder with a molten resin reservoir used when repelling waste plastic.

Self Resilience ability of Waste Plastics

Dimaleimide-substituted tetraphenylethene (TPE-2MI), which is non-emissive due to photo-induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was synthesized and used to cross-link random copolymers of methyl, decyl, or lauryl methacrylate with furfuryl methacrylate. The mixture of the copolymers and TPE-2MI in DMF showed reversible fluorescence with “turn on/off” behavior depending on the Diels–Alder (DA)/retro-DA temperature adjustable process. At high temperatures, the retro-DA reaction dominates, and the fluorescence is quenched by PET mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE-2MI polymer film was prepared to show an accurate response to the external temperature with tunable fluorescent “turn on/off” behavior. This study proposes possible applications in areas such as information security and transmission.

Diels–Alder Polymer Networks with Temperature-Reversible Cross-Linking-Induced Emission

Hydroxyapatite (HA) is a calcium phosphate bioreactive and biocompatible material which is an essential element for bone regeneration in human and animal bodies. HA can be found abundant in bones and shells of aquatic animals. The extraction or recovery of HA from aquatic species play an important role in future biomedical applications such as drug delivery, implant coatings, scaffolds for bone grafts, etc. [1]. Therefore, in our study, a wet chemical method was utilized for extraction of HA from bones of different types of seafood wastes (Oreochromis spp, Channa striata, Thunnus albacares, Notopterus notopterus, Salmo salar, Pangasius krempfi). The extracted HA powders were characterized by different characterization methods such as FTIR, XRD, Optical microscope and ICP-MS. Their bioactivity was also evaluated by the immersion of HA powders in stimulated body fluids. The results showed that the extracted HA powders from bones of Channa striata species had the best biocompability and be a good candidate material for bone regeneration, particularly when they existed at a nano-scaled size.

Recovery of Hydroxyapatite From Bones of Seafood Wastes and Its Bioactivity Evaluation

The increasing contamination of organic micropollutants in environmental and biological systems is one of the serious issues faced by humanity. The potentially harmful effects of organic micropollutants (pesticides, pharmaceuticals, and dyes) on human health and aquatic ecosystems have raised worldwide concerns. The releasing of organic micropollutants to freshwater causes serious health hazards because most of them are mutagenic or carcinogenic in nature. Comparing with absorbents, membrane technology possesses merits of high separation performance, low energy consumption, mild operation temperature, cost efficiency, and no cross-contamination, etc.
Here, we propose 2D covalent organic framework (COF) membranes for molecular separation. Azobenzene derivatives act as linkers, which can be photo-switched between trans- and cis-isomers by irradiation under ultraviolet (UV) or visible light. The resultant smart COF membrane has nanopores that can be switched between On- (big pores) and Off-state (small pores) valves for molecular separation. The COF membranes were tested in different organic solvents and exhibit permeances as high as 56.7 L m-2 h-1 bar-1, in the following order: acetonitrile > acetone > methanol > ethanol > isopropanol > DMF. Interestingly, the smart cis-COF membranes with Off-state valves under UV show higher rejection for dye molecules than the trans-COF analogue with On-state valves. Different from the traditional membranes with immutable pore channels, the pore size of COF membranes can be remotely tuned by controlling the trans-to-cis isomerization of azobenzene via UV/Vis light, therefore, the permeance and separation factor can be adjusted as needed.
The ingenious design strategy endows traditional membranes with new fascination and opens up new perspectives for separation science and technology. The development of COF based smart membranes with a periodic honeycomb lattice could be a promising solution for a wide variety of separations such as catalyst and solvent recycle, wastewater treatment (organic micropollutant or heavy metal removal), valuable drug purification from organic solvents in pharmaceutical industry (vitamin or antibiotic refinement), oil extraction and purification in food industry, and other challenging separations (hemodialysis or chiral pharmacology separation).

Smart light-responsive COF membrane for molecular separation

Concerns over dwindling oil reserves, carbon dioxide emissions from fossil fuel sources and associated climate change is driving the need for clean, renewable energy supplies. If average global temperature rises induced by greenhouse gases are not to exceed 1.5 °C, then estimates indicate that a large proportion of crude oil, gas and coal reserves must remain untouched.1 Biomass, derived from agricultural and forestry residues, or non-food sources of triglycerides are a sustainable source of carbon that can provide low cost solutions for transportation fuels and organic chemicals. Akin to petroleum refining, biorefining will integrate biomass conversion processes to produce fuels, power, and chemicals, thereby increasing the economic viability of bio-derived processes. Indeed, the US DoE identified a range of sugar derived ‘Platform Chemicals’ produced via chemical or biochemical transformation of lignocellulosic biomass as potential targets for manufacture in biorefineries.2 Catalytic technologies played a critical role in the economic development of both the petrochemical industry and modern society, underpinning 90 % of chemical processes and contributing to over 20% of all industrial products. In a post-petroleum era, catalysis will underpin biorefinery technology, and researchers will need to rise to the challenge of synthesising chemical intermediates and advanced functional materials and fuels from such non-petroleum based feedstocks.3 

This presentation will discuss the challenges faced in catalytic biomass processing, and highlight recent successes in catalyst design facilitated by advances in nanotechnology and careful tuning of catalyst formulation. Specific case studies will explore (i) how the effects of pore architecture and acid strength can impact upon process efficiency in biodiesel synthesis;4,5 (ii) how catalytic pre-treatments improve transportation fuel production from pyrolysis oil,6 and (iii) the role of bifunctional catalysts in the hydrodeoxygenation of phenolic components in bio-oils,7 and the aqueous phase processing of sugars to important platform chemicals and fuel precursors such as 5-HMF derivatives.8



References. 
1. M. Jakob, J. Hilaire, Nature, 517 (2015) 150.
2. J.J. Bozell, G.R. Petersen, Green Chemistry, 12 (2010) 539.
3. K. Wilson, A. F. Lee Phil. Trans. R. Soc. A, 374 (2016) 20150081.
4. A.F. Lee, K Wilson, Catalysis Today, 242 (2015) 3. 
5. M.A. Isaacs, C.M.A. Parlett, N. Robinson, L.J. Durndell, J.C. Manayil, S.K. Beaumont, S. Jiang, N.S. Hondow, A.C. Lamb, M.L. Johns, K. Wilson, A.F. Lee, Nature Catalysis, 3 (2020), 921.
6. L. Ciddor, J.A. Bennett, J.A. Hunns, K. Wilson, A.F. Lee J. Chem. Tech. Biotech., 90 (2015) 780. 
7. A. Shivhare, J.A. Hunns, L.J. Durndell, C.M.A. Parlett, M.A. Isaacs, A.F. Lee, K. Wilson, ChemSusChem, 13 (2020), 4771.
8. A. Osatiashtiani, A.F. Lee, D.R. Brown, J.A. Melero, G. Morales, K. Wilson, Cat. Sci. Tech., 4 (2014), 333. 


Catalysts for a Sustainable Future

Sulfur-containing polymer is promising to the application of the optical, anti-corrosion and antifouling materials. Using sulfur-containing C1 building blocks [i.e. carbonyl sulfide (COS), carbon disulfide (CS2)] to copolymerize with epoxides have been rapidly developed in our group and others. This talk reports two metal-free routes for the reaction of COS with epoxides.
1) The inhibition of oxygen-sulfur exchange reaction (O-S ER)1 for synthesizing poly(monothiocarbonate)s. Two types of organocatalysts will present, one is the combination of Lewis bases including amidine, guanidine, or quaternary onium salts with triethyl borane.2 A highly transparent and colorless poly(monothiocarbonate)s are obtained with > 99% tail-to-head content and high Mns of up to 92.5 kg/mol. O-S ER that would generate random thiocarbonate and carbonate units, were totally suppressed in most instances. The turnover frequency (TOF) of these Lewis pairs are as high as 240 h-1 at ambient temperature. The other is the combination of organic bases and thioureas via cooperative catalysis.3 Poly(monothiocarbonate)s are obtained with 100 % alternating degree, > 99% tail-to-head content, high Mns of up to 98.4 kg/mol and narrow molecular weight distributions (1.13-1.23). TOFs of the catalysts are up to 112 h−1 at 25 °C. 
2) The utilization of O-S ER for synthesizing poly(thioether)s using COS and epoxides as the starting materials.4 This route undergoes the coupling reaction of COS with epoxides, decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing CO2(a little bit COS). And this method is also applied to the reaction of carbon disufide with epoxides, providing a new pathway to produce COS and poly(thioether)s simultaneously. 
Finally, we’ll present the transformation of poly(monothiocarbonate)s to poly(thioether)s by using O-S ER process, which is a polymer A to polymer B method for recycling the polymers.

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Simultaneous and efficient removal of Cr(VI) and methyl orange on layered double hydroxides decorated porous carbons

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Simultaneous and efficient removal of Cr(VI) and methyl orange on layered double hydroxides decorated porous carbons