Moving beyond bimetallic-alloy to single-atom dimer atomic-interface for all-pH hydrogen evolution

Single-atom-catalysts (SACs) afford a fascinating activity with respect to other nanomaterials for hydrogen evolution reaction (HER), yet the simplicity of single-atom center limits its further modification and utilization. Obtaining bimetallic single-atom-dimer (SAD) structures can reform the electronic structure of SACs with added atomic-level synergistic effect, further improving HER kinetics beyond SACs. However, the synthesis and identification of such SAD structure remains conceptually challenging. Herein, systematic first-principle screening reveals that the synergistic interaction at the NiCo-SAD atomic interface can upshift the d-band center, thereby, facilitate rapid water-dissociation and optimal proton adsorption, accelerating alkaline/acidic HER kinetics. Inspired by theoretical predictions, we develop a facile strategy to obtain NiCo-SAD on N-doped carbon (NiCo-SAD-NC) via in-situ trapping of metal ions followed by pyrolysis with precisely controlled N-moieties. X-ray absorption spectroscopy indicates the emergence of Ni-Co coordination at the atomic-level. The obtained NiCo-SAD-NC exhibits exceptional pH-universal HER-activity, demanding only 54.7 and 61 mV overpotentials at −10 mA cm−2 in acidic and alkaline media, respectively. This work provides a facile synthetic strategy for SAD catalysts and sheds light on the fundamentals of structure-activity relationships for future applications.

A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution

Hydrogen spillover phenomenon of metal-supported electrocatalysts can significantly impact their activity in hydrogen evolution reaction (HER). However, design of active electrocatalysts faces grand challenges due to the insufficient understandings on how to overcome this thermodynamically and kinetically adverse process. Here we theoretically profile that the interfacial charge accumulation induces by the large work function difference between metal and support (∆Φ) and sequentially strong interfacial proton adsorption construct a high energy barrier for hydrogen transfer. Theoretical simulations and control experiments rationalize that small ∆Φ induces interfacial charge dilution and relocation, thereby weakening interfacial proton adsorption and enabling efficient hydrogen spillover for HER. Experimentally, a series of Pt alloys-CoP catalysts with tailorable ∆Φ show a strong ∆Φ-dependent HER activity, in which PtIr/CoP with the smallest ∆Φ = 0.02 eV delivers the best HER performance. These findings have conclusively identified ∆Φ as the criterion in guiding the design of hydrogen spillover-based binary HER electrocatalysts.

Enhanced interfacial electron transfer between thylakoids and RuO2 nanosheets for photosynthetic energy harvesting

The harvesting of photosynthetic electrons (PEs) directly from photosynthetic complexes has been demonstrated over the past decade. However, their limited efficiency and stability have hampered further practical development. For example, despite its importance, the interfacial electron transfer between the photosynthetic apparatus and the electrode has received little attention. In this study, we modified electrodes with RuO2 nanosheets to enhance the extraction of PEs from thylakoids, and the PE transfer was promoted by proton adsorption and surface polarity characteristics. The adsorbed protons maintained the potential of an electrode more positive, and the surface polarity enhanced thylakoid attachment to the electrode in addition to promoting ensemble docking between the redox species and the electrode. The RuO2 bioanode exhibited a five times larger current density and a four times larger power density than the Au bioanode. Last, the electric calculators were successfully powered by photosynthetic energy using a RuO2 bioanode.

Anomalous low impedance for small platinum microelectrodes

Electrical measurement of the activity of individual neurons is a primary goal for many invasive neural electrodes. Making these “single unit” measurements requires that we fabricate electrodes small enough so that only a few neurons contribute to the signal, but not so small that the impedance of the electrode creates overwhelming noise or signal attenuation. Thus, neural electrode design often must strike a balance between electrode size and electrode impedance, where the impedance is often assumed to scale linearly with electrode area. Here we test this assumption by measuring the impedance at 1 kHz for differently sized electrodes. Surprisingly, we find that for Pt electrodes (but not Au electrodes) this assumption breaks down for electrodes with diameters of less than 10 microns. For these small sizes, Pt electrodes have impedance values that are up to 3-fold lower than expected. By investigating the impedance spectrum of Pt and Au electrodes we find a transition between planar and spherical diffusion for small electrodes combined with the pseudo-capacitance of proton adsorption at the Pt surface can explain this anomalous low impedance. These results provide important intuition for designing small, single unit recording electrodes. Specifically, for materials that have a pseudo-capacitance or when diffusional capacitance dominates the total impedance, we should expect small electrodes will have lower-than-expected impedance values allowing us to scale these devices down further than previously thought before thermal noise or voltage division limits the ability to acquire high-quality single-unit recordings.

A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution

Hydrogen spillover phenomenon of metal-supported electrocatalysts can significantly impact their activity in hydrogen evolution reaction (HER). However, design of active electrocatalysts faces grand challenges due to the insufficient understandings on how to overcome this thermodynamically and kinetically adverse process. We theoretically profile that the interfacial charge accumulation induced by the large work function difference between metal and support (∆Φ) and sequentially strong interfacial proton adsorption construct a high energy barrier for hydrogen transfer. Theoretical simulations and control experiments rationalize that small ∆Φ induces interfacial charge dilution and relocation, thereby weakening interfacial proton adsorption and enabling efficient hydrogen spillover for HER. Experimentally, a series of Pt alloys-CoP catalysts with tailorable ∆Φ showed a strong ∆Φ-dependent HER activity, in which PtIr/CoP with the smallest ∆Φ = 0.02 eV delivered the best HER performance. These findings have conclusively identified ∆Φ as the criterion in guiding the design of hydrogen spillover-based binary HER electrocatalysts.