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ABSTRACT: We review in this Viewpoint recent progress on the development of a new class of sustainable electrocatalytic systems for water-splitting and molecular hydrogen generation using diiron disulfide ([2Fe-2S]) active site methacrylate metallopolymers. To date, noble metal catalysts (e.g, platinum) remain the best electrocatalysts for molecular hydrogen generation using water as the chemical feedstock and proton donor. However, there remains a need for the synthesis of efficient electrocatalytic systems using low cost, earth abundant materials for sustainable H2 generation. We focus on our recent work in this area using well-defined single site [2Fe-2S]-metallopolymer catalysts. Thus far, these systems have demonstrated rates of hydrogen production >25 times faster than [FeFe]-hydrogenase enzymes and match the current densities of platinum with only 0.2 V higher potential when operating in water at neutral pH with tris(hydroxymethyl)aminoethane (TRIS) buffer (Faradaic yields 100±3%). The molecular design and synthesis of [2Fe-2S]-metallopolymers are reviewed along with mechanistic studies unraveling the causality of efficient H2 production from this catalytic system. The overall current output and overpotential are improved by (a) the reversible electrostatic adsorption of the metallopolymer on the carbon electrode surface that enhances the proton and electron transfer rates and (b) the use of protic buffer electrolytes (PBEs) that enhance the availability of protons. The schemes summarized here to improve the performance of [2Fe-2S] catalysts by incorporation into metallopolymers may be used to enhance the performance of other molecular electrocatalysts at the electrode surface. 

ABSTRACT: The diverse functionalization of the polymeric support phase of diiron disulfide[2Fe–2S] metallopolymer elec-trocatalysts offers a route to enhanced generation of molecular hydrogen production via water-splitting. Click chemistry has been shown to be a useful tool in post-polymerization functionalization for a wide range of polymeric materials under mild conditions which is a requirement for [2Fe-2S] metallopolymers due to the presence of iron carbonyl (Fe-CO) bonds in the active site. In this study, we developed a new synthetic methodology to functionalize [2Fe–2S] metallopolymers using atom transfer radical polymerization (ATRP) and post-polymerization functionalization using azide-alkyne “click” cycloaddition. Azide functional [2Fe–2S] metallopolymers were prepared by the ATRP of 3-azidopropyl methacrylate (AzPMA) with either methyl methacrylate (MMA), or 2-(dimethylamino)ethyl methacrylate (DMAEMA), followed by copper-catalyzed “click” cycloaddition with functional terminal alkynes. Both families of PMMA and PDMAEMA functional [2Fe–2S] metallo-co-polymers were found to be retain Fe-CO bonds from the catalyst active site after the click chemistry reactions, and more importantly, exhibited high electrocatalytic activity for electrochemical water-splitting under pH neutral aqueous conditions.Not Available 

The preparation of sulfur containing polymers from inexpensive, commodity sulfur base chemicals is an emerging field of polymer chemistry as a route to consume elemental sulfur generated from fossil fuel refining. Recently a new process, termed, sulfenyl chloride inverse vulcanization has been developed that exploits the high reactivity and miscibility of sulfur monochloride, (S2Cl2) with a broad range of allylic monomers to prepare soluble, high molar mass linear polymers, segmented block copolymers and crosslinked thermosets with greater synthetic precision than achieved using classical inverse vulcanization with elemental sulfur. However, the ring opening of episulfonium intermediates from this polymerization can proceed via Markovnikov, anti-Markovnikov, or alternative pathways resulting in complex regioisomeric microstructures, particularly when used with allylic ester monomers. Hence, to accelerate structural characterization of this new class of polyhalodisulfides prepared by the sulfenyl chloride inverse vulcanization process, we report on a detailed structural characterization to quantify the molar composition of regioisomeric units in these materials using NMR spectroscopy,focusing on sulfenyl chloride additions to allylic benzoate substrates. We report on a general methodologyusing one- and two-dimensional NMR spectroscopic techniques to enable direct integration of 2D NMRspectroscopic cross peaks to quantify the molar composition of regioisomeric units in 1,3-diallyl isophthalate(DAI) polymerized with S2Cl2, along with detailed studies on model compound reactions to detail the analytical methodology. 

Chalcogenide hybrid inorganic/organic polymers (CHIPs) are a new class of optical polymeric materials for imaging and photonic applications due to their high refractive indices and high optical transmission at visible and infrared wavelengths. In this study, we characterize these polymers to study the refractive index and delve into the electronic properties by way of measurements of their dielectric constants. Ellipsometry is used to determine the refractive indices for wavelengths from 500 nm to 12 µm, while we use capacitance measurements on thin film capacitors with a range of areas to find the dielectric constant. The results are in line with expectations based on the sulfur composition of the polymers-indices range from 1.7 to 1.85, and dielectric constants range from 2.6 to 3. With these measurements, these sulfur polymer materials are established to be good candidates for optical and photonic applications, particularly with respect to telecommunications. The dielectric constants suggest that applications such as electro-optic devices and capacitors may also be viable. 

A molecular catalyst attached to an electrode sur-face can in principle offer the advantages of both homogeneous and heterogeneous catalysis. Unfortunately, some molecular catalysts constrained to a surface lose much or all of their solution performance. In contrast, we have found that when a small molecule [2Fe–2S] catalyst is incorporated into metallopolymers of the form PDMAEMA–g–[2Fe–2S] (PDMAEMA = poly(2-dimethylamino)ethyl methacrylate) and adsorbed to the sur-face, the observed rate of hydrogen production increases to kobs > 105 s-1 per active site with lower overpotential, increased life-time, and tolerance to oxygen. Herein, the electrocatalytic performances of these metallopolymers with different length polymer chains are compared to reveal the factors that lead to this high performance. It was anticipated that smaller metallopolymers would have faster rates due to faster electron and proton transfers to more accessible active sites, but the experiments show that the rates of catalysis per active site are largely independent of the polymer size. Molecular dynamics modelling reveals that the high performance is a consequence of adsorption of these metallopolymers on the surface with natural assembly that brings the [2Fe–2S] catalytic sites into close contact with the electrode surface while maintaining exposure of the sites to protons in solution. The assembly is conducive to fast electron transfer, fast proton transfer, and a high rate of catalysis regardless of polymer size. These results offer a guide to enhancing the performance of other electrocatalysts with incorporation into a polymer that provides optimal interaction of the catalyst with the electrode and with solution. 

Abstract Multiple relaxation times are used to capture the numerous stress relaxation modes found in bulk polymer melts. Herein, inverse vulcanization is used to synthesize high sulfur content (≥50 wt%) polymers that only need a single relaxation time to describe their stress relaxation. The S-S bonds in these organopolysulfides undergo dissociative bond exchange when exposed to elevated temperatures, making the bond exchange dominate the stress relaxation. Through the introduction of a dimeric norbornadiene crosslinker that improves thermomechanical properties, we show that it is possible for the Maxwell model of viscoelasticity to describe both dissociative covalent adaptable networks and living polymers, which is one of the few experimental realizations of a Maxwellian material. Rheological master curves utilizing time-temperature superposition were constructed using relaxation times as nonarbitrary horizontal shift factors. Despite advances in inverse vulcanization, this is the first complete characterization of the rheological properties of this class of unique polymeric material.