Electrocatalytic [FeFe]-hydrogenase mimics for the hydrogen evolution reaction (HER) generally suffer from low activity, high overpotential, aggregation, oxygen sensitivity, and low solubility in water. By using atom-transfer radical polymerization (ATRP), a new class of [FeFe]-metallopolymers with precise molar mass, defined composition, and low polydispersity, has been prepared. The synthetic methodology introduced here allows facile variation of polymer composition to optimize the [FeFe] solubility, activity, and long-term chemical and aerobic stability. Water soluble functional metallopolymers facilitate electrocatalytic hydrogen production in neutral water with loadings as low as 2 ppm and operate at rates an order of magnitude faster than hydrogenases (2.5×10 s ), and with low overpotential requirement. Furthermore, unlike the hydrogenases, these systems are insensitive to oxygen during catalysis, with turnover numbers on the order of 40 000 under both anaerobic and aerobic conditions.

Reviewed herein is the development of novel polymer‐supported [2Fe‐2S] catalyst systems for electrocatalytic and photocatalytic hydrogen evolution reactions. [FeFe] hydrogenases are the best known naturally occurring metalloenzymes for hydrogen generation, and small‐molecule, [2Fe‐2S]‐containing mimetics of the active site (H‐cluster) of these metalloenzymes have been synthesized for years. These small [2Fe‐2S] complexes have not yet reached the same capacity as that of enzymes for hydrogen production. Recently, modern polymer chemistry has been utilized to construct an outer coordination sphere around the [2Fe‐2S] clusters to provide site isolation, water solubility, and improved catalytic activity. In this review, the various macromolecular motifs and the catalytic properties of these polymer‐supported [2Fe‐2S] materials are surveyed. The most recent catalysts that incorporate a single [2Fe‐2S] complex, termed single‐site [2Fe‐2S] metallopolymers, exhibit superior activity for H2 production.

The tetrafluorinated derivative of 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), is of interest for charge transfer complex formation and as a p-dopant in organic electronic materials. Fourier transform infrared (FTIR) spectroscopy is commonly employed to understand the redox properties of F4TCNQ in the matrix of interest; specifically, the ν­(CN) region of the F4TCNQ spectrum is exquisitely sensitive to the nature of the charge transfer between F4TCNQ and its matrix. However, little work has been done to understand how these vibrational modes change in the presence of possible acid/base chemistry. Here, FTIR spectroelectrochemistry is coupled with density functional theory spectral simulation for study of the electrochemically generated F4TCNQ radical anion and dianion species and their protonation products with acids. Vibrational modes of HF4TCNQ–, formed by proton-coupled electron transfer, are identified, and we demonstrate that this species is readily formed by strong acids, such as trifluoroacetic acid, and to a lesser extent, by weak acids, such as water. The implications of this chemistry for use of F4TCNQ as a p-dopant in organic electronic materials is discussed.

Electrocatalytic generation of H2 is challenging in neutral pH water, where high catalytic currents for the hydrogen evolution reaction (HER) are particularly sensitive to the proton source and solution characteristics. A tris(hydroxymethyl)aminomethane (TRIS) solution at pH 7 with a [2Fe-2S]-metallopolymer electrocatalyst gave catalytic current densities around two orders of magnitude greater than either a more conventional sodium phosphate solution or a potassium chloride (KCl) electrolyte solution. For a planar polycrystalline Pt disk electrode, a TRIS solution at pH 7 increased the catalytic current densities for H2 generation by 50 mA/cm2 at current densities over 100 mA/cm2 compared to a sodium phosphate solution. As a special feature of this study, TRIS is acting not only as the primary source of protons and the buffer of the pH, but the protonated TRIS ([TRIS-H]+) is also the sole cation of the electrolyte. A species that is simultaneously the proton source, buffer, and sole electrolyte is termed a protic buffer electrolyte (PBE). The structure–activity relationships of the TRIS PBE that increase the HER rate of the metallopolymer and platinum catalysts are discussed. These results suggest that appropriately designed PBEs can improve HER rates of any homogeneous or heterogeneous electrocatalyst system. General guidelines for selecting a PBE to improve the catalytic current density of HER systems are offered.

Small-molecule catalysts inspired by the active sites of [FeFe]-hydrogenase enzymes have long struggled to achieve fast rates of hydrogen evolution, long-term stability, water solubility, and oxygen compatibility. We profoundly improved on these deficiencies by grafting polymers from a metalloinitiator containing a [2Fe-2S] moiety to form water-soluble poly­(2-dimethylamino)­ethyl methacrylate metallopolymers (PDMAEMA-g-[2Fe-2S]) using atom transfer radical polymerization (ATRP). This study illustrates the critical role of the polymer composition in enhancing hydrogen evolution and aerobic stability by comparing the catalytic activity of PDMAEMA-g-[2Fe-2S] with a nonionic water-soluble metallopolymer based on poly­(oligo­(ethylene glycol) methacrylate) prepared via ATRP (POEGMA-g-[2Fe-2S]) with the same [2Fe-2S] metalloinitiator. Additionally, the tunability of catalyst activity is demonstrated by the synthesis of metallocopolymers incorporating the 2-(dimethylamino)­ethyl methacrylate (DMAEMA) and oligo­(ethylene glycol) methacrylate (OEGMA) monomers. Electrochemical investigations into these metallo­(co)­polymers show that PDMAEMA-g-[2Fe-2S] retains complete aerobic stability with catalytic current densities in excess of 20 mA·cm–2, while POEGMA-g-[2Fe-2S] fails to reach 1 mA·cm–2 current density even with the application of high overpotentials (η > 0.8 V) and loses all activity in the presence of oxygen. Random copolymers of the two monomers polymerized with the same [2Fe-2S] initiator showed intermediate activity in terms of current density, overpotential, and aerobic stability.

Electrocatalytic [FeFe]-hydrogenase mimics for the hydrogen evolution reaction (HER) generally suffer from low activity,h igh overpotential, aggregation, oxygen sensitivity, and low solubility in water.B yu sing atom-transfer radical polymerization (ATRP), an ew class of [FeFe]-metallopolymers with precise molar mass,d efined composition, and low polydispersity,h as been prepared. The synthetic methodology introduced here allows facile variation of polymer composition to optimize the [FeFe] solubility,a ctivity,a nd long-term chemical and aerobic stability.W ater soluble functional metallopolymers facilitate electrocatalytic hydrogen production in neutral water with loadings as low as 2ppm and operate at rates an order of magnitude faster than hydrogenases (2.5 10 5 s À1 ), and with lowoverpotential requirement. Furthermore, unlike the hydrogenases,these systems are insensitive to oxygen during catalysis,with turnover numbers on the order of 40 000 under both anaerobic and aerobic conditions.

Reviewed herein is the development of novel polymer‐supported [2Fe‐2S] catalyst systems for electrocatalytic and photocatalytic hydrogen evolution reactions. [FeFe] hydrogenases are the best known naturally occurring metalloenzymes for hydrogen generation, and small‐molecule, [2Fe‐2S]‐containing mimetics of the active site (H‐cluster) of these metalloenzymes have been synthesized for years. These small [2Fe‐2S] complexes have not yet reached the same capacity as that of enzymes for hydrogen production. Recently, modern polymer chemistry has been utilized to construct an outer coordination sphere around the [2Fe‐2S] clusters to provide site isolation, water solubility, and improved catalytic activity. In this review, the various macromolecular motifs and the catalytic properties of these polymer‐supported [2Fe‐2S] materials are surveyed. The most recent catalysts that incorporate a single [2Fe‐2S] complex, termed single‐site [2Fe‐2S] metallopolymers, exhibit superior activity for H2 production.

No abstract