Well supported: Stable hemin–graphene conjugates (see picture) formed by immobilization of monomeric hemin on graphene, showed excellent catalytic activity, more than 10 times better than that of the recently developed hemin–hydrogel system and 100 times better than that of unsupported hemin. The catalysts also showed excellent binding affinities and catalytic efficiencies approaching that of natural enzymes.

Transition-metal phosphides have been shown to be promising electrocatalysts in water for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). To maximize reactivity toward both entails limiting the catalyst size while maintaining reactivity and avoiding aggregation. Frame-like hollow nanostructures (nanoframes) provide the required open structure with sufficient channels into the interior volume. We demonstrate here the design and synthesis of CoP nanoframes (CoP NFs) by a strategy involving precipitation, chemical etching, and low-temperature phosphidation steps. It results in impressive bifunctional catalytic activities for both HER and OER and consequently enables a highly efficient water electrolyzer with a current density of 10 mA cm–2 driven by a cell voltage of only 1.65 V. The strategy has been generalized for the preparation of nanoframe Co dichalcogenides CoX2 NFs, with X = S, Se, and Te. The results of electrochemical measurements, supported by density functional theory calculations, show that HER catalytic activities for the series follow the sequence: CoP NFs > CoSe2 NFs > CoS2 NFs > CoTe2 NFs.

Real-time monitoring of nitric oxide concentrations is of central importance for probing the diverse roles of nitric oxide in neurotransmission, cardiovascular systems and immune responses. Here we report a new design of nitric oxide sensors based on hemin-functionalized graphene field-effect transistors. With its single atom thickness and the highest carrier mobility among all materials, graphene holds the promise for unprecedented sensitivity for molecular sensing. The non-covalent functionalization through p-p stacking interaction allows reliable immobilization of hemin molecules on graphene without damaging the graphene lattice to ensure the highly sensitive and specific detection of nitric oxide. Our studies demonstrate that the graphene-hemin sensors can respond rapidly to nitric oxide in physiological environments with a sub-nanomolar sensitivity. Furthermore, in vitro studies show that the graphene-hemin sensors can be used for the detection of nitric oxide released from macrophage cells and endothelial cells, demonstrating their practical functionality in complex biological systems.

The integration of multiple synergistic catalytic systems can enable the creation of biocompatible enzymatic mimics for cascading reactions under physiologically relevant conditions. Here we report the design of a graphene–haemin–glucose oxidase conjugate as a tandem catalyst, in which graphene functions as a unique support to integrate molecular catalyst haemin and enzymatic catalyst glucose oxidase for biomimetic generation of antithrombotic species. Monomeric haemin can be conjugated with graphene through π–π interactions to function as an effective catalyst for the oxidation of endogenous L-arginine by hydrogen peroxide. Furthermore, glucose oxidase can be covalently linked onto graphene for local generation of hydrogen peroxide through the oxidation of blood glucose. Thus, the integrated graphene–haemin–glucose oxidase catalysts can readily enable the continuous generation of nitroxyl, an antithrombotic species, from physiologically abundant glucose and L-arginine. Finally, we demonstrate that the conjugates can be embedded within polyurethane to create a long-lasting antithrombotic coating for blood-contacting biomedical devices.

Molybdenum (Mo) carbide-based electrocatalysts are considered promising candidates to replace Pt-based materials toward the hydrogen evolution reaction (HER). Among different crystal phases of Mo carbides, although MoC exhibits the highest catalytic performance, the activity is still restricted by the strong Mo-H bonding. To weaken the strong Mo-H bonding, creating abundant MoC/MoC interfaces and/or doping a proper amount of electron-rich (such as N and P) dopants into the MoC crystal lattice are effective because of the electron transfer from Mo to surrounding C in carbides and/or N/P dopants. In addition, Mo carbides with well-defined nanostructures, such as one-dimensional nanostructure, are desirable to achieve abundant catalytic active sites. Herein, well-defined N,P-codoped MoC/MoC nanofibers (N,P-Mo C NF) were prepared by pyrolysis of phosphomolybdic ([PMoO], PMo) acid-doped polyaniline nanofibers at 900 °C under an Ar atmosphere, in which the hybrid polymeric precursor was synthesized via a facile interfacial polymerization method. The experimental results indicate that the judicious choice of pyrolysis temperature is essential for creating abundant MoC/MoC interfaces and regulating the N,P-doping level in both Mo carbides and carbon matrixes, which leads to optimized electronic properties for accelerating HER kinetics. As a result, N,P-Mo C NF exhibits excellent HER catalytic activity in both acidic and alkaline media. It requires an overpotential of only 107 and 135 mV to reach a current density of 10 mA cm in 0.5 M HSO and 1 M KOH, respectively, which is comparable and even superior to the best of Mo carbide-based electrocatalysts and other noble metal-free electrocatalysts.