On-chip electrocatalytic microdevices.

On-chip electrocatalytic microdevices (OCEMs) are an emerging electrochemical platform specialized for investigating nanocatalysts at the microscopic level. The OCEM platform allows high-precision electrochemical measurements at the individual nanomaterial level and, more importantly, offers unique perspectives inaccessible with conventional electrochemical methods. This protocol describes the critical concepts, experimental standardization, operational principles and data analysis of OCEMs. Specifically, standard protocols for the measurement of the electrocatalytic hydrogen evolution reaction of individual 2D nanosheets are introduced with data validation, interpretation and benchmarking. A series of factors (e.g., the exposed area of material, the choice of passivation layer and current leakage) that could have effects on the accuracy and reliability of measurement are discussed. In addition, as an example of the high adaptability of OCEMs, the protocol for in situ electrical transport measurement is detailed. We believe that this protocol will promote the general adoption of the OCEM platform and inspire further development in the near future. This protocol requires essential knowledge in chemical synthesis, device fabrication and electrochemistry.

Boosting the performance of single-atom catalysts via external electric field polarization.

Single-atom catalysts represent a unique catalytic system with high atomic utilization and tunable reaction pathway. Despite current successes in their optimization and tailoring through structural and synthetic innovations, there is a lack of dynamic modulation approach for the single-atom catalysis. Inspired by the electrostatic interaction within specific natural enzymes, here we show the performance of model single-atom catalysts anchored on two-dimensional atomic crystals can be systematically and efficiently tuned by oriented external electric fields. Superior electrocatalytic performance have been achieved in single-atom catalysts under electrostatic modulations. Theoretical investigations suggest a universal "onsite electrostatic polarization" mechanism, in which electrostatic fields significantly polarize charge distributions at the single-atom sites and alter the kinetics of the rate determining steps, leading to boosted reaction performances. Such field-induced on-site polarization offers a unique strategy for simulating the catalytic processes in natural enzyme systems with quantitative, precise and dynamic external electric fields.

Single-Atom Tailoring of Two-Dimensional Atomic Crystals Enables Highly Efficient Detection and Pattern Recognition of Chemical Vapors.

Low-dimensional semiconductor materials, such as single-walled carbon nanotubes, two-dimensional (2D) atomic crystals, and organic frameworks, have been widely adapted as ideal platforms to construct various chemo/biosensors with satisfying sensitivity. However, the general drawbacks in chemiresistive devices, including high operation temperatures, low response to low-polarity molecules, and poor selectivity, have limited their real-world applications. In this study, 2D materials (graphene, MoS2, and WSe2) were systematically functionalized with series of monodispersed single atomic sites (Pt, Co, and Ru) through a facile approach to construct single-atom sensors (SASs) for the detection of VOCs at room temperature. The structural and catalytic characteristics of SAs successfully translated into enhanced gas-sensing performance, with a 1-2 orders of magnitude increase in relative response to ethanol (@5 ppm) and acetone (@20 ppm) vapors (in all M-2D SASs as compared to pristine substrates), high selectivity to VOCs against relative humidity (M-WSe2 SASs), and fast response/recovery time (11/58 s for Pt-Graphene and 22/48 s for Pt-MoS2 to 50 ppm ethanol, 9/57 s for Pt-Graphene and 15/75 s for Pt-MoS2 to 200 ppm acetone) that are several times faster than the pristine 2D materials. Density functional theory (DFT) calculations revealed the signaling mechanism in SASs, and the data were further trained to build machine learning (ML) models for predicting the adsorption energies and sensing performance using the features of adsorption heights, metal charge, and charge transfer between the adsorbed VOCs and SASs sites. Finally, the rich combination of the metal single atoms and 2D atomic crystal supports were converted to cross-sensitive SA sensor array that allows for detection and identification of different VOCs.

Double-Exchange-Induced in situ Conductivity in Nickel-Based Oxyhydroxides: An Effective Descriptor for Electrocatalytic Oxygen Evolution.

Motivated by in silico predictions that Co, Rh, and Ir dopants would lead to low overpotentials to improve OER activity of Ni-based hydroxides, we report here an experimental confirmation on the altered OER activities for a series of metals (Mo, W, Fe, Ru, Co, Rh, Ir) doped into γ-NiOOH. The in situ electrical conductivity for metal doped γ-NiOOH correlates well with the trend in enhanced OER activities. Density functional theory (DFT) calculations were used to rationalize the in situ conductivity of the key intermediate states of metal doped γ-NiOOH during OER. The simultaneous increase of OER activity with intermediate conductivity was later rationalized by their intrinsic connections to the double exchange (DE) interaction between adjacent metal ions with various d orbital occupancies, serving as an indicator for the key metal-oxo radical character, and an effective descriptor for the mechanistic evaluation and theoretical guidance in design and screening of efficient OER catalysts.

Deactivation/Activation of Quenching Defects in CH3NH3PbI3 Perovskite by Direct Electron Injection/Extraction.

Organometal halide perovskites (OMHPs) have emerged as advisible materials for application in optoelectronic devices over the past decade. However, a variety of complex slow responses in OMHPs under an external electric field have been observed, and the mechanisms for these responses remain a topic of intense debate. In this work, with an external voltage applied to the CH3NH3PbI3 crystal, reversible photoluminescence (PL) enhancement and quenching behaviors respectively near the anode and the cathode were observed under wide-field fluorescence microscopy. Further experiments attribute the reversible PL enhancing responses to the electron injection effect increasing the radiative recombination, while PL quenching was attributed to be due to the electron extraction effect increasing the nonradiative recombination. The control of PL by external applied voltage indicates brilliant carrier mobility in the CH3NH3PbI3 crystal and also reminds us to focus on the effect of hole/electron injection on the materials which may limit the performance of perovskite-based optoelectronic devices.

On-Chip Electrical Transport Investigation of Metal Nanoparticles: Characteristic Acidic and Alkaline Adsorptions Revealed on Pt and Au Surface.

Metal nanocrystals have been extensively explored as efficient and tailorable electrocatalysts for various sustainable energy technologies. Precise understanding of molecular interactions at the electrode-electrolyte interfaces during electrochemical processes, which mostly relies on the interpretation of spectroscopic surface information, is crucial to the innovations in catalyst design and optimization of reaction conditions. Here, we demonstrate the first in situ electrical transport evidence of pH-dependent surface anionic adsorptions on metal nanoparticles (MNPs), enabled by the on-chip electrical transport spectroscopy (ETS) of continuous nanoparticle (NP) thin films. Our results on platinum and gold NPs reveal the significant (and distinct) impacts of acid-base environments on their surface adsorption features, which contributes to the further understanding of gold- and platinum-based electrocatalytic systems. The successful employment of ETS on metal nanoparticles achieves a more general transport-based signaling technique that conveniently fits the abundance of catalytic materials with zero-dimension morphology.