The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen.

The excellent catalytic activity of metallic MoS2 edges for the hydrogen evolution reaction (HER) has led to substantial efforts towards increasing the edge concentration. The 2H basal plane is less active for the HER because it is less conducting and therefore possesses less efficient charge transfer kinetics. Here we show that the activity of the 2H basal planes of monolayer MoS2 nanosheets can be made comparable to state-of-the-art catalytic properties of metallic edges and the 1T phase by improving the electrical coupling between the substrate and the catalyst so that electron injection from the electrode and transport to the catalyst active site is facilitated. Phase-engineered low-resistance contacts on monolayer 2H-phase MoS2 basal plane lead to higher efficiency of charge injection in the nanosheets so that its intrinsic activity towards the HER can be measured. We demonstrate that onset potentials and Tafel slopes of ∼-0.1 V and ∼50 mV per decade can be achieved from 2H-phase catalysts where only the basal plane is exposed. We show that efficient charge injection and the presence of naturally occurring sulfur vacancies are responsible for the observed increase in catalytic activity of the 2H basal plane. Our results provide new insights into the role of contact resistance and charge transport on the performance of two-dimensional MoS2 nanosheet catalysts for the HER.

One-Step Laser Nanostructuration of Reduced Graphene Oxide Films Embedding Metal Nanoparticles for Sensing Applications.

The combination of two-dimensional materials and metal nanoparticles (MNPs) allows the fabrication of novel nanocomposites with unique physical/chemical properties exploitable in high-performance smart devices and biosensing strategies. Current methods to obtain graphene-based films decorated with noble MNPs are cumbersome, poorly reproducible, and difficult to scale up. Herein, we propose a straightforward, versatile, surfactant-free, and single-step technique to produce reduced graphene oxide (rGO) conductive films integrating "naked" noble MNPs. This method relies on the instantaneous laser-induced co-reduction of graphene oxide and metal cations, resulting in highly exfoliated rGO nanosheets embedding gold, silver, and platinum NPs. The production procedure has been optimized, and the obtained nanomaterials are fully characterized; the hybrid nanosheets have been easily transferred onto lab-made screen-printed electrodes preserving their nanoarchitecture. The Au@rGO-, Ag@rGO-, and Pt@rGO-based electrodes have been challenged to detect caffeic acid, nitrite, and hydrogen peroxide in model solutions and real samples. The sensors yielded quantitative responses (R2 ≥ 0.997) with sub-micromolar limits of detections (LODs ≤ 0.6 µM) for all the analytes, allowing accurate quantification in samples (recoveries ≥ 90%; RSD ≤ 14.8%, n = 3). This single-step protocol which requires low cost and minimal equipment will allow the fabrication of free-standing, MNP-embedded rGO films integrable into a variety of scalable smart devices and biosensors.

Laser Reduced Graphene Oxide Electrode for Pathogenic Escherichia coli Detection.

Graphene-based materials are of interest in electrochemical biosensing due to their unique properties, such as high surface areas, unique electrochemical properties, and biocompatibility. However, the scalable production of graphene electrodes remains a challenge; it is typically slow, expensive, and inefficient. Herein, we reported a simple, fast, and maskless method for large-scale, low-cost reduced graphene oxide electrode fabrication; using direct writing (laser scribing and inkjet printing) coupled with a stamp-transferring method. In this process, graphene oxide is simultaneously reduced and patterned with a laser, before being press-stamped onto polyester sheets. The transferred electrodes were characterized by SEM, XPS, Raman, and electrochemical methods. The biosensing utility of the electrodes was demonstrated by developing an electrochemical test for Escherichia coli. These biosensors exhibited a wide dynamic range (917-2.1 × 107 CFU/mL) of low limits of detection (283 CFU/mL) using just 5 µL of sample. The test was also verified in spiked artificial urine, and the sensor was integrated into a portable wireless system driven and measured by a smartphone. This work demonstrates the potential to use these biosensors for real-world, point-of-care applications. Hypothetically, the devices are suitable for the detection of other pathogenic bacteria.

A plug, print & play inkjet printing and impedance-based biosensing technology operating through a smartphone for clinical diagnostics.

Simplicity is one of the key feature for the spread of any successful technological product. Here, a method for rapid and low-cost fabrication of electrochemical biosensors is presented. This "plug, print & play" method involves inkjet-printing even in an office-like environment, without the need of highly specialized expertise or equipment, guaranteeing an ultra-fast idea to (scaled) prototype production time. The printed biosensors can be connected to a smartphone through its audio input for their impedance readout, demonstrating the validity of the system for point-of-care biosensing. Proper electrodes layout guarantees high sensitivity and is validated by finite element simulations. The introduction of a passivation method (wax printing) allowed to complete the devices fabrication process, increasing their sensitivity. Indeed, the wax allowed reducing the interference related to the parasitic currents flowing through the permeable coating of the employed substrates, which was used for the chemical sintering, thus avoiding the common thermal treatment after printing. As a case study, we used the devices to develop an electrochemical aptamer-based sensor for the rapid detection of neutrophil gelatinase-associated lipocalin (NGAL) in urine - a clinically important marker of acute kidney injury. The aptasensor platform is capable of detecting clinically relevant concentrations of NGAL with a simple and rapid smartphone readout. The developed technology may be extended in the future to continuous monitoring, taking advantage of its flexibility to integrate it in tubes, or to other diagnostic applications where cost/efficiency and rapidity of the research, development and implementation of point of care devices is a must.