Graphene is regarded as a potential surface-enhanced Raman spectroscopy (SERS) substrate. However, the application of graphene quantum dots (GQDs) has had limited success due to material quality. Here, we develop a quasi-equilibrium plasma-enhanced chemical vapor deposition method to produce high-quality ultra-clean GQDs with sizes down to 2 nm directly on SiO2/Si, which are used as SERS substrates. The enhancement factor, which depends on the GQD size, is higher than conventional graphene sheets with sensitivity down to 1 × 10−9 mol L−1 rhodamine. This is attributed to the high-quality GQDs with atomically clean surfaces and large number of edges, as well as the enhanced charge transfer between molecules and GQDs with appropriate diameters due to the existence of Van Hove singularities in the electronic density of states. This work demonstrates a sensitive SERS substrate, and is valuable for applications of GQDs in graphene-based photonics and optoelectronics.

Electrochemical water splitting requires efficient, low‐cost water oxidation catalysts to accelerate the sluggish kinetics of the water oxidation reaction. A rapid photocorrosion method is now used to synthesize the homogeneous amorphous nanocages of Cu‐Ni‐Fe hydr(oxy)oxide as a highly efficient electrocatalyst for the oxygen evolution reaction (OER). The as‐fabricated product exhibits a low overpotential of 224 mV on a glassy carbon electrode at 10 mA cm−2 (even lower down to 181 mV when supported on Ni foam) with a Tafel slope of 44 mV dec−1 for OER in an alkaline solution. The obtained catalyst shows an extraordinarily large mass activity of 1464.5 A g−1 at overpotential of 300 mV, which is the highest mass activity for OER. This synthetic strategy may open a brand new pathway to prepare copper‐based ternary amorphous nanocages for greatly enhanced oxygen evolution.

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We report the use of surface-enhanced Raman scattering (SERS) to measure the vibrational Stark shifts of surface-bound thiolated-benzonitrile molecules bound to an electrode surface during hydrogen evolution reactions (HERs). Here, the electrode surface consists of Au nanoislands deposited both with and without an underlying layer of monolayer graphene on a glass substrate. The Stark shifts observed in the nitrile (C-N) stretch frequency (around 2225 cm) are used to report the local electric field strength at the electrode surface under electrochemical working conditions. Under positive (i.e., oxidative) applied potentials [vs normal hydrogen electrode (NHE)], we observe blue shifts of up to 7.6 cm, which correspond to local electric fields of 22 mV/cm. Under negative applied potentials (vs NHE), the C-N stretch frequency is red-shifted by only about 1 cm. This corresponds to a regime in which the electrochemical current increases exponentially in the hydrogen evolution process. Under these finite electrochemical currents, we estimate the voltage drop across the solution ( V = IR). Correcting for this voltage drop results in a highly linear electric field versus applied electrochemical voltage relation. Here, the onset potential for the HER lies around 0.2 V versus NHE and the point of zero charge (PZC) occurs at 0.04 V versus NHE, based on the capacitance-voltage ( C- V) profile. The solution field is obtained by comparing the C-N stretch frequency in solution with that obtained in air. By evaluating the local electric field strength at the PZC and the onset potential, we can separate the solution field from the reaction field (i.e., electrode field), respectively. At the onset of HER, the solution field is -0.8 mV/cm and the electrode field is -1.2 mV/cm. At higher ion concentrations, we observe similar electric field strengths and more linear E-field versus applied potential behavior because of the relatively low resistance of the solution, which results in negligible voltage drops ( V = IR).