High Thermopower in a Zn-Based 3D Semiconductive Metal-Organic Framework.

Conductive metal-organic frameworks (c-MOFs) have drawn increasing attention for their outstanding performance in energy-related applications. However, the majority of reported c-MOFs are based on 2D structures. Synthetic strategies for 3D c-MOFs are under-explored, leaving unrealized functionality in both their structures and properties. Herein we report Zn-HAB, a 3D c-MOF comprised of hexaaminobenzene and Zn(II). Zn-HAB is shown to have microporosity with a band gap of approximately 1.68 eV, resulting in a moderate conductivity of 0.86 mS cm-1 and a high Seebeck coefficient of 200 µV K-1 at 300 K. The power factor of 3.44 nW m-1 K-2 constitutes the first report of the thermoelectric properties of an intrinsically conductive 3D MOF.

Air-Stability and Carrier Type in Conductive M3(Hexaaminobenzene)2, (M = Co, Ni, Cu).

Herein, we investigate the effects of changing the metal ions in the M-HAB system, with HAB = hexaaminobenzene ligands and M = Co, Ni, Cu. The phyiscal characteristics of this MOF family are insensitive to changes in the metal cation, which enables systematic evaluation of the effect of metal cation identity on electrical transport properties. We observe that the metal ion profoundly influences the electrical conductivity and dominant carrier type in the resulting MOF and the air-stability thereof. Cu-HAB and Co-HAB are determined to exhibit n-type conduction under both ambient and nitrogen conditions; Ni-HAB is found to be ambipolar, with its dominant carrier type dramatically affected by the environment. We examine these results through calculation of the band structure, the partial density of states, and charge transfer analysis. Unlike traditional conductive organic materials, we find that the air-stability is not well predicted by the LUMO level of these n-type MOFs but instead is additionally dependent on the occupancy and orientation of the metal ion's d-orbitals and the resulting interaction between the metal ion and ligand. This study provides fundamental insights for rational design of air-stable, electronically conductive MOFs.

Biodegradable and flexible arterial-pulse sensor for the wireless monitoring of blood flow.

The ability to monitor blood flow is critical to patient recovery and patient outcomes after complex reconstructive surgeries. Clinically available wired implantable monitoring technology requires careful fixation for accurate detection and needs to be removed after use. Here, we report the design of a pressure sensor, made entirely of biodegradable materials and based on fringe-field capacitor technology, for measuring arterial blood flow in both contact and non-contact modes. The sensor is operated wirelessly through inductive coupling, has minimal hysteresis, fast response times, excellent cycling stability, is highly robust, allows for easy mounting and eliminates the need for removal, thus reducing the risk of vessel trauma. We demonstrate the operation of the sensor with a custom-made artificial artery model and in vivo in rats. This technology may be advantageous in real-time post-operative monitoring of blood flow after reconstructive surgery.

Synthetic Routes for a 2D Semiconductive Copper Hexahydroxybenzene Metal-Organic Framework.

Conductive metal-organic frameworks (c-MOFs) have shown outstanding performance in energy storage and electrocatalysis. Varying the bridging metal species and the coordinating atom are versatile approaches to tune their intrinsic electronic properties in c-MOFs. Herein we report the first synthesis of the oxygen analog of M3(C6X6)2 (X = NH, S) family using Cu(II) and hexahydroxybenzene (HHB), namely Cu-HHB [Cu3(C6O6)2], through a kinetically controlled approach with a competing coordination reagent. We also successfully demonstrate an economical synthetic approach using tetrahydroxyquinone as the starting material. Cu-HHB was found to have a partially eclipsed packing between adjacent 2D layers and a bandgap of approximately 1 eV. The addition of Cu-HHB to the family of synthetically realized M3(C6X6)2 c-MOFs will enable greater understanding of the influence of the organic linkers and metals, and further broadens the range of applications for these materials.

Stabilization of Hexaaminobenzene in a 2D Conductive Metal-Organic Framework for High Power Sodium Storage.

Redox-active organic materials have gained growing attention as electrodes of rechargeable batteries. However, their key limitations are the low electronic conductivity and limited chemical and structural stability under redox conditions. Herein, we report a new cobalt-based 2D conductive metal-organic framework (MOF), Co-HAB, having stable, accessible, dense active sites for high-power energy storage device through conjugative coordination between a redox-active linker, hexaaminobenzene (HAB), and a Co(II) center. Given the exceptional capability of Co-HAB for stabilizing reactive HAB, a reversible three-electron redox reaction per HAB was successfully demonstrated for the first time, thereby presenting a promising new electrode material for sodium-ion storage. Specifically, through synthetic tunability of Co-HAB, the bulk electrical conductivity of 1.57 S cm-1 was achieved, enabling an extremely high rate capability, delivering 214 mAh g-1 within 7 min or 152 mAh g-1 in 45 s. Meanwhile, an almost linear increase of the areal capacity upon increasing active mass loading up to 9.6 mg cm-2 was obtained, demonstrating 2.6 mAh cm-2 with a trace amount of conducting agent.

Investigation of a Solution-Processable, Nonspecific Surface Modifier for Low Cost, High Work Function Electrodes.

We demonstrate the ability of the highly fluorinated, chemically inert copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) to significantly increase the work function of a variety of common electrode materials. The work function change is hypothesized to occur via physisorption of the polymer layer and formation of a surface dipole at the polymer/conductor interface. When incorporated into organic solar cells, an interlayer of PVDF-HFP at an Ag anode increases the open circuit voltage by 0.4 eV and improves device power conversion efficiency by approximately an order of magnitude relative to Ag alone. Solution-processable in air, PVDF-HFP thin films provide one possible route toward achieving low cost, nonreactive, high work function electrodes.

Polymer Electrolyte Membrane Electrolyzers Utilizing Non-precious Mo-based Hydrogen Evolution Catalysts.

The development of low-cost hydrogen evolution reaction (HER) catalysts that can be readily integrated into electrolyzers is critical if H2 from renewable electricity-powered electrolysis is to compete cost effectively with steam reforming. Herein, we report three distinct earth-abundant Mo-based catalysts, namely those based on MoSx , [Mo3 S13 ](2-) nanoclusters, and sulfur-doped Mo phosphide (MoP|S), loaded onto carbon supports. The catalysts were synthesized through facile impregnation-sulfidization routes specifically designed for catalyst-device compatibility. Fundamental electrochemical studies demonstrate the excellent HER activity and stability of the Mo-sulfide based catalysts in an acidic environment, and the resulting polymer electrolyte membrane (PEM) electrolyzers that integrate these catalysts exhibit high efficiency and durability. This work is an important step towards the goal of replacing Pt with earth-abundant catalysts for the HER in commercial PEM electrolyzers.

Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes.

Understanding molecular recognition is of fundamental importance in applications such as therapeutics, chemical catalysis and sensor design. The most common recognition motifs involve biological macromolecules such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific molecule. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chemical adsorption, also form a new corona phase that exhibits highly selective recognition for specific molecules. To prove the generality of this phenomenon, we report three examples of heteropolymer-nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodynamic model of surface interactions in which the dissociation constants can be tuned by perturbing the chemical structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-infrared, as we show by tracking riboflavin diffusion in murine macrophages.