Ionically Cross‐Linked Proton Conducting Membranes for Fuel Cells

For improving stability without sacrificing ionic conductivity, ionically cross‐linked proton conducting membranes are fabricated from Na⁺‐form sulfonated poly(phthalazinone ether sulfone kentone) (SPPESK) and H⁺‐formed sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO). Ionically acid‐base cross‐linking between sulfonic acid groups in SPPO and phthalazone groups in SPPESK impart the composite membranes the good miscibility and electrochemical performance. In particular, the composite membranes possess proton conductivity of 60–110 mS cm⁻¹ at 30 °C. By controlling the protonation degree of SPPO within 40–100 %, the composite membranes with favorable cross‐linking degree are qualified for application in fuel cells. The maximum power density of the composite membrane reaches approximately 1100 mW cm⁻² at the current density of 2800 mA cm⁻² at 70 °C.     

Ion‐exchange membranes prepared by blending sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) with polybenzimidazole

New ion‐exchange acid/base‐blend (SPPO/PBI) membranes were prepared by mixing N,N‐dimethylacetamide (DMA) solutions of sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO) in the ammonium form and of polybenzimidazole (PBI), casting the solution as a thin film, evaporating the solvent, and treating the membrane with aqueous hydrochloric acid. The resulting membranes were found insoluble in DMA. The preliminary tests of the membranes were carried out in an H₂/O₂ fuel cell at room temperature. Their performance in the fuel cell increased with the increase in the concentration of SPPO sulfonic acid groups in the blend, but the membranes formed with the highly sulfonated SPPO alone or predominanting, which swelled excessively in water, did not give reproducible results, and their performance was usually inferior to that of the membranes having an optimum ratio of both components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1118–1127, 2002     

Fundamental studies of homogeneous cation exchange membranes from poly(2,6‐dimethyl‐1,4‐phenylene oxide): Membranes prepared by simultaneous aryl‐sulfonation and aryl‐bromination

Strong acid homogenous cation exchange membranes were obtained by simultaneously introducing sulfonic and bromine groups into poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO). The ion‐exchange capacity (IEC), water content, transport number, diffusion coefficient, contact angle, and tensile strength of the obtained membranes were studied. The results show that the membrane intrinsic properties are largely dependent on the substitution of bromine: the IEC and water content decrease with bromine content, while the area resistance and permselectivity of the membranes increase with this trend. Therefore, by properly balancing them, a series of homogenous cation exchange membranes having good electrical properties and physical stability can be obtained to comply with different industrial electromembrane processes, such as diffusion dialysis, electrodialysis, electrodeionization, etc. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2238–2243, 2006     

Microporous membranes prepared from blends of polysulfone and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide)

Membranes were prepared from solutions containing Udel‐type polysulfone (PSf) and sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO). Polymer solutions in 1‐methyl‐2‐pyrrolidone were cast on a nonwoven textile and precipitated in a water bath. The permeabilities and selectivities of the prepared membranes depended on the concentrations of both polymers in the casting solution. The higher the concentration of PSf, the lower were the permeabilities to water and average pore sizes of the membranes. On the other hand, a very small amount of SPPO in the casting solution (about 1–4 wt % relative to the casting solution weight) brought about a considerable increase in water permeabilities and had a small influence on the average pore sizes. The effects were most pronounced if SPPO with a degree of sulfonation of 20–40% was used. The considerable increase in water permeabilities was explained by separation of the PSf and SPPO phases during precipitation in water and by the concentration of hydrophilic SPPO on the surface of the membrane and its pores. The determinations of the oriented concentration potentials proved the presence of a negative surface charge in the membranes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 134–142, 2001     

Partially Sulfonated Poly(1,4‐phenylene ether‐ether‐sulfone) and Poly(vinylidene fluoride) Blend Membranes for Fuel Cells

Blend membranes based on high conductive sulfonated poly(1,4‐phenylene ether‐ether‐sulfone) (SPEES) and poly(vinylidene fluoride) (PVDF) having excellent chemical stability were prepared and characterized for direct methanol fuel cells. The effects of PVDF content on the proton conductivity, water uptake, and chemical stability of SPEES/PVDF blend membranes were investigated. The morphology, miscibility, thermal, and mechanical properties of blend membranes were also studied by means of scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) measurements. The blend membrane containing 90 wt.% SPEES (degree of sulfonation – DS = 72%) and 10 wt.% PVDF (M_w = 180,000) exhibits optimum properties among various SPEES72/PVDF membranes. Addition of PVDF enhanced resistance of the SPEES membrane against peroxide radicals and methanol significantly without deterioration of its proton conductivity. It's proton conductivity at 80 °C and 100% relative humidity is higher than Nafion 115 while it's methanol permeability is only half of that of Nafion 115 at 80 °C. The direct methanol fuel cell performance of the SPEES membranes was better than that of Nafion 115 membrane at 80 °C.     

Composite Membrane of Sulfonated Poly (phenylene oxide) Doped with Phosphosilicate Gels for Direct Methanol Fuel Cell

Summary The newly developed composite membranes of sulfonated poly (phenylene oxide) (SPPO) doped with phosphosilicate gel were prepared for direct methanol fuel cell (DMFC). SPPO with higher ion exchange capacity (IEC) value (IEC=2.83 mequiv./g) was chosen as polymer matrix, and the phosphosilicate gel with P/Si equal to 1.5 was employed as dopant. Sulfonation of PPO was confirmed by FT-IR and ¹H NMR. And the morphology characterization of sol particles with different stirring time was done by TEM. Moreover, the surface morphology of composite membranes was characterized by SEM. As for methanol permeability (P_M) and proton conductivity (σ), it was demonstrated that all composite membranes were displaying lower methanol permeability than Nafion^?112 and comparable conductivity to Nafion^?112 at room temperature under hydration state. When it comes to selectivity parameter (Φ=σ/P_M), composite membranes show higher Φ values than Nafion^?112, and the highest value is 4.70, 5.6 times higher than 0.845 of Nafion^?112. It is implied that the composite membranes will be the promising membrane material used in DMFC.     

Thermal,mechanical, and morphological characterization studies of poly(2,6‐dimethyl‐1,4‐phenylene oxide) blends with polystyrene and brominated polystyrene

The miscibility of the binary and ternary blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide), brominated polystyrene, and polystyrene was investigated using a differential scanning calorimeter. The morphology of these blends was characterized by scanning electron microscopy. These studies revealed a close relation between the blend structure and its mechanical properties. The compatibilizing effect of poly(2,6‐dimethyl‐1,4‐phenylene oxide) on the miscibility of the polystyrene/brominated polystyrene blends was examined. It was found that poly(2,6‐dimethyl‐1,4‐phenylene oxide), which was miscible with polystyrene and partially miscible with brominated polystyrene, compatibilizes these two immiscible polymers if its contention exceeds 33 wt %. Upon the addition of poly(2,6‐dimethyl‐1,4‐phenylene oxide) to the immiscible blends of polystyrene/brominated polystyrene, we observed a change in the morphology of the mixtures. An improvement in the mechanical properties was noticed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 225–231, 2000     

Free‐standing hybrid anion‐exchange membranes for application in fuel cells

A series of free‐standing hybrid anion‐exchange membranes were prepared by blending brominated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (BPPO) with poly(vinylbenzyl chloride‐co‐γ‐methacryloxypropyl trimethoxy silane) (poly(VBC‐co‐γ‐MPS)). Apart from a good compatibility between organic and inorganic phases, the hybrid membranes had a water uptake of 32.4–51.8%, tensile strength around 30 MPa, and T_d temperature at 5% weight loss around 243–261°C. As compared with the membrane prepared from poly (VBC‐co‐γ‐MPS), the hybrid membranes exhibited much better flexibility, and larger ion‐exchange capacity (2.19–2.27 mmol g^?1) and hydroxyl (OH^?) conductivity (0.0067–0.012 S cm^?1). In particular, the hybrid membranes with 60–75 wt % BPPO had the optimum water uptake, miscibility between components, and OH^? conductivity, and were promising for application in fuel cells. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Quaternized poly(phenylene oxide) anion exchange membrane for alkaline direct methanol fuel cells in KOH‐free media

A series of anion exchange membrane (AEM) electrolytes with quaternary ammonium moiety are fabricated from poly (phenylene oxide) for its application in alkaline direct methanol fuel cells (ADMFCs). In the first step, poly(phenylene oxide) (PPO) is successfully chloromethylated by substituting chloromethyl groups in the aryl position of polymer. In the second step, the chloromethylated PPO (CPPO) is further homogeneously quaternized and ion‐exchanged to form an AEM. From the second step, series of AEMs are prepared by changing the mole ratio of amine in relation to CPPO. The presence of quaternary ammonium group in the membrane was confirmed by elemental analysis. The fabricated membranes are subjected to cell polarization studies in ADMFCs, wherein quaternized poly(2,6‐dimethyl‐1,4‐phenylene oxide) (CPPO:amine of 1:8) membrane exhibits higher peak power density of 3.5 mW cm^?2 when compared with the other ratios of CPPO:amine in the absence of KOH solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43693.     

Partial crosslinking method for poly(2,6‐dimethyl‐1,4‐phenylene oxide)–poly(vinyl alcohol) membranes to obtain optimized stability and permeability

A partial crosslinking method was developed to modify hydrophilic membranes. The membrane was sandwiched between two porous plates to protect part of the areas, then immersed into a crosslinking solution such as glutaraldehyde, and finally, set free from the plates. The protected and unprotected areas were alternatively distributed to form a heterogeneous membrane. The unprotected areas were crosslinked to enhance the membrane stability, whereas the protected areas retained their original permeability. Three types of hydrophilic base membranes were selected and prepared from poly(2,6‐dimethyl‐1,4‐phenylene oxide) and poly(vinyl alcohol). The base membranes were partially crosslinked (5.56% of the direct area with enlarged areas) to investigate their stability and diffusion dialysis (DD) performances. The partially crosslinked membranes had remarkably reduced water uptake and swelling degrees compared with the base membranes (72.4–250.4 vs 178.2%–544.4% and 94.0%–408.0% vs. 163.8%–814.8%). Meanwhile, the membranes still retained high DD performances for separating HCl–FeCl₂ or NaOH–NaAlO₂ solutions. The dialysis coefficients of HCl and NaOH were much higher than those of the fully crosslinked membranes (0.0209 vs. 0.0109 m/h and 0.0059–0.0085 vs. 0.0017–0.0022 m/h). Hence, partial crosslinking was effective in optimizing the membrane hydrophilicity and permeability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45305.     

Novel imidazole‐grafted hybrid anion exchange membranes based on poly(2,6‐dimethyl‐1,4‐phenylene oxide) for fuel cell applications

Novel organic–inorganic hybrid membranes, based on poly(2,6‐dimethyl‐1,4‐phenylene oxide), have been prepared through 1,2‐dimethylimidazole functional groups and double crosslinking agents including 3‐glycidyloxypropyltrimethoxysilane and tetraethyl orthosilicate by sol–gel process for the purpose of improving the conductivity and alkaline resistance. The structure of membranes was characterized using Fourier‐transform infrared spectra, ¹H NMR, and X‐ray diffraction. The physico‐chemical properties of all membranes were shown in ion exchange capacity, water uptake, stability, and conductivity. Membranes with OH^– conductivity up to 0.022 at 25 °C and 0.036 S cm^?1 at 80 °C. Promisingly, the chemical stability of the resulting membranes remains unchanged after storage in 2 mol dm^?3 KOH at 25 °C over at least 10 days. The tensile strength can be higher than 30 MPa, and the elongation at break (Eb) is in the range 6.68–10.84%. Hence, this hybrid membrane can be potentially applied in alkaline fuel cells. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46034.     

Influence of chemical compositions on the properties of random and multiblock sulfonated poly(arylene ether sulfone)‐based proton‐exchange membranes

The influence of chemical compositions on the properties of sulfonated poly(arylene ether sulfone)‐based proton‐exchange membranes was studied. First, we synthesized three different series of random SPAES copolymers using three kinds of hydrophobic monomers, including 4,4′‐dihydroxyldiphenylether, 2,6‐dihydroxynaphthalene (DHN), and 4,4′‐hexafluoroisopropylidenediphenol (6F‐BPA) to investigate effects of hydrophobic components on the properties of SPAES membranes as proton‐exchange membranes. Random SPAES copolymers with 6F‐BPA showed the highest proton conductivity while random SPAES copolymers with DHN displayed the lowest methanol permeability among the three random copolymers. Subsequently, we synthesized multiblock SPAES using the DHN as a hydrophobic monomer and studied the effect of the length of hydrophilic segments in the multiblock SPAES copolymers on membrane performance. The results indicated that longer hydrophilic segments in the copolymers led to higher water uptake, proton conductivity, and proton/methanol selectivity of membranes even at low humidity. In addition, the morphology studies (AFM and SAXS measurements) of membranes suggested that multiblock copolymers with long hydrophilic segments resulted in developed phase separation in membranes, and ionic clusters formed more easily, thus improving the membrane performance. Therefore, both the kinds of hydrophobic monomers and the length of hydrophilic segments in SPAES copolymers would influence the membranes performance as proton‐exchange membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of semi-interpenetrating polymer networks with adjustable mesh width and hydrophobicity

Proton exchange membranes (PEMs) with a semi-interpenetrating polymer network (SIPN) structure were prepared by cross-linking brominated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) with different aliphatic α,ω-diamine cross-linkers in the presence of sulfonated PPO (SPPO). The alkylation of the α,ω-diamine with BPPO resulted in a covalently cross-linked BPPO network where SPPO could be immobilized by interlocking. The interlocked structure was also strengthened by ion pair interactions between the sulfonic acid groups of SPPO and the amine moieties formed in cross-linking. The length of the aliphatic α,ω-diamine cross-linker was varied to modify the hydrophobicity and the mesh width (the average distance between two cross-linked polymer segments) of the cross-linked network host. The effects of these adjustments on the structure of the cross-linked network host were evaluated by the morphology of the hydrophilic domains, and transport properties such as proton conductivity and methanol permeability. It was found that the increase in mesh width and hydrophobicity of networks formed by long cross-linkers resulted in more scattered hydrophilic domains and fewer contiguous connections. On the contrary, the hydrophilic domains in networks with short cross-linkers were closer and more extensively-connected to facilitate proton transport. Methanol crossover in the SIPN membranes, on the other hand, could be suppressed by downsizing the size of the hydrophilic domains. Overall water uptake and dimensional swelling of the membranes were also affected by the cross-linker length. Some of the SIPN membranes delivered better performance than the Nafion^® 117 membrane in single stack fuel cell tests, demonstrating the potential of SIPNs for the construction of fuel cell PEMs.     

Characterization of random and multiblock copolymers of highly sulfonated poly(arylene ether sulfone) for a proton‐exchange membrane

Random and multiblock copolymers of sulfonated poly(arylene ether sulfone) (SPAES) were synthesized and characterized to compare the differences in the properties of proton‐exchange membranes made with random and multiblock SPAES copolymers. Atomic force microscopy observations and small‐angle X‐ray scattering measurements suggested the presence of nanoscale, clusterlike structures in the multiblock SPAES copolymers but not in the random SPAES copolymers. Proton‐exchange membranes were prepared from random and multiblock copolymers with various ion‐exchange capacities (IECs). The water uptake, proton conductivity, and methanol permeability of the SPAES membranes depended on the IECs of the random and multiblock SPAES copolymers. At the same IEC, the multiblock SPAES copolymers exhibited higher performances with respect to proton conductivity and proton/methanol permeation selectivity than the random SPAES copolymers. The higher performances of the multiblock SPAES copolymers were thought to be due to their clusterlike structure, which was similar to the ionic cluster of a Nafion membrane. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Proton conductivity and methanol permeability of sulfonated poly(vinyl alcohol) membranes modified by using sulfoacetic acid and poly(acrylic acid)

Sulfonated poly(vinyl alcohol) (PVA) for use as a proton conductive membrane in a direct methanol fuel cell (DMFC) was prepared by reacting the PVA with sulfoacetic acid and poly(acrylic acid). The effects of the amount of sulfoacetic acid and poly(acrylic acid) on proton conductivity, methanol permeability, water uptake, and ion exchange capacity (IEC) of the sulfonated PVA membranes were investigated by using impedance analysis, gas chromatography, gravimetric analysis, and titration techniques, respectively. The water uptake of the membranes decreased with the amount of the sulfoacetic acid and the amount of poly(acrylic acid) used. The proton conductivity and the IEC values of the membranes initially increased and then decreased with the amount of the sulfoacetic acid. The methanol permeability of the sulfonated PVA membranes decreased continuously with the amount of the sulfoacetic acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Novel hollow‐fiber anion‐exchange hybrid membranes: Preparation and characterization

To develop ion‐exchange membranes for application in severe conditions, such as those with high temperatures, strongly oxidizing environments, or organic solvents, new hollow‐fiber anion‐exchange hybrid membranes were prepared by the immersion of brominated poly(2,6‐dimethyl‐1,4‐phenylene oxide) base hollow fibers in a tetraethoxysilane–ethanol solution followed by sol–gel and quaternary amination. Compared to conventional polymeric charged membranes, the prepared hybrid membranes were higher in both thermal and dimensional stabilities. The results suggest that tetraethoxysilane concentration was an important factor affecting the membrane's intrinsic properties. When the tetraethoxysilane concentration was in the range 15–45%, the final hollow‐fiber anion‐exchange hybrid membranes had an ion‐exchange capacity of 1.9–2.0 mmol/g, a water uptake of.83–1.23 g of water/g of dry weight, and a dimensional change ratio of 13–18%. An evaluation on the membranes' separation performances is underway. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cross‐linked Poly(arylene ether ketone) Proton Exchange Membranes with High Ion Exchange Capacity for Fuel Cells

Sulfonated poly(arylene ether ketone) (SPAEK) possessing the pendant carboxylic acid groups was synthesized. The carboxylic acid groups of SPAEK were reacted with a cross‐linking reagent to prepare a cross‐linked membrane with a high ion exchange capacity (IEC), a high oxidative stability, and an excellent mechanical strength. The cross‐linking hindered the mobility of the polymer chains and thus strongly affected the water uptake and the methanol permeability of the membranes. Also, as the cross‐linker used in this study bore sulfonic acid groups, cross‐linking did not lead to a noticeable loss of the proton conductivity. The cross‐linked SPAEK membrane with 20% cross‐linking density, CSPAEK‐20% membrane, exhibited a high proton conductivity of 0.045 S cm^–1 associated with a high IEC value of 1.78 mmol g^–1 but a low methanol permeability of 4.3 × 10^–7 cm² s^–1. The CSPAEK‐20% membrane also showed excellent cell performance and oxidation resistance.     

Synthesis and Characterisation of Sulphonated Poly(arylene sulphone) Terpolymers with Triphenylphosphine Oxide Moieties for Proton Exchange Membrane Fuel Cells

For application in fuel cells, a series of sulphonated poly(phenylene sulphone) terpolymers with triphenylphosphine oxide moieties as constitutional units in the polymer backbone have been prepared. The synthesis of the terpolymers represents a two‐step process including: (i) an aromatic nucleophilic substitution polycondensation of three difluoro monomers with varying ratios, i.e. 3,3′‐disulphonate‐4,4′‐difluorodiphenylsulphone, 4,4′‐difluorodiphenylsulphone and bis(4‐fluorophenyl)phenyl phosphine oxide (BFPPO), with 4,4′‐thiobisbenzenethiol yielding sulphonated poly(phenylene sulphide) terpolymers (sPPSPO) and (ii) their following oxidation with hydrogen peroxide in acidic solution to yield sulphonated poly(phenylene sulphone) terpolymers (sPPSO2PO). The structures and molecular compositions were confirmed by ¹H and ¹³C NMR spectroscopy. The ion exchange capacity (IEC) was adjusted at will choosing the appropriate ratio of sulphonated and unsulphonated monomers. Terpolymers with 1.72 ≤ IEC ≤ 2.32 have been obtained. Sulphonated poly(arylene) ionomers containing only sulphone (–SO₂–) linkages and phosphine oxide (–PO–) units rather than ether or sulphide in the backbone reveal a high thermal and oxidative stability. Membranes were cast either from dimethylformamide (DMF) or from dimethyl sulphoxide (DMSO) solutions. For all terpolymers some general characteristic trends were observed, such as an increase of the proton conductivity with increasing IEC, water uptake and temperature. The series of sPPSO2PO membranes offered high conductivities at high humidification, however, their performance strongly depends on the relative humidity. The mechanical properties of sulphonated poly(phenylene sulphone)s have been considerably improved by means of terpolymerisation with phenylene oxide moieties. Even under high humidification the terpolymers form clear, flexible membranes the stress at break of some membranes exceeds that of Nafion® under the same conditions by 40%.     

Transport properties of sulfonated poly (styrene‐isobutylene‐styrene) membranes with counter‐ion substitution

In this study, the transport properties of poly(styrene‐isobutylene‐styrene) (SIBS) were determined as a function of sulfonation level (0–94.9%) and counter‐ion substitution (Ba⁺², Ca⁺², Mg⁺², Mn⁺², Cu⁺², K⁺¹) for fuel cell applications. Increasing the sulfonation level improved the ion exchange capacity (IEC) of the membranes up a maximum (1.71 mequiv/g), suggesting a complex three‐dimensional network at high sulfonation levels. Results show that proton conductivity increases with IEC and is very sensitive to hydration levels. Methanol permeability, although also sensitive to IEC, shows a different behavior than proton conductivity, suggesting fundamental differences in their transport mechanism. The incorporation of counter‐ion substitution decreases both methanol and proton transport. Methanol permeability seems to be related to the size of the counter‐ion studied, while proton conductivity is more sensitive to water content, which is also reduced upon the incorporation of counter‐ions. To complement the studies, selectivity (i.e., proton conductivity/methanol permeability) of the studied membranes was determined and compared to Nafion® 117. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication and investigation of phosphoric acid doped imidazolium siloxane crosslinked poly(2,6‐dimethyl‐1,4‐phenylene oxide) for high temperature polymer electrolyte membranes

A series of high temperature polymer electrolyte membranes were fabricated based on imidazolium poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) using methylimidazole (MeIm) and triethoxysilylpropyldihydroimidazole (SiIm) as quaternization reagents via the S_N2 nucleophilic substitution. Meanwhile SiIm was also employed as a crosslinking agent and the crosslinked Si–O–Si network was constructed through a hydrolysis procedure of SiIm in an acid medium. Compared with the PPO‐100%MeIm membrane without the crosslinking structure, the imidazolium siloxane crosslinked PPO‐x%SiIm‐y%MeIm membranes exhibited increased acid doping contents, enhanced dimensional stabilities, improved mechanical properties and higher conductivities. The PPO‐30%SiIm‐70%MeIm/(198 wt% phosphoric acid) membrane displayed a conductivity of 0.08 S cm^?1 at 180 °C without humidifying and a tensile strength of 6.4 MPa at room temperature. © 2019 Society of Chemical Industry