Electrochemical Microscopy Based on Spatial Light Modulators: A Projection System to Spatially Address Electrochemical Reactions at Semiconductors

Here we describe a “light projector” system that can address, i.e. “read and write” electrochemical reactions on a non-structured macroscopic semiconducting electrode with spatial and temporal resolution. In our approach the illumination of an amorphous silicon electrode/electrolyte interface is spatially defined by means of a ferroelectric micromirror system that gives total freedom on both the two-dimensional light profile (illumination shapes) as well as on the transient times of the projected images. The device has no moving parts and allows for spatial and temporal control of the illumination stimulus driving local changes to the rate of an electrochemical reaction. The performance of the system is assessed by generating microscale patterns of Cu2O on the electrode (“electrochemical writing”) followed by their 2D current mapping (“electrochemical reading”) using methanol electro-oxidation and carbon dioxide electro-reduction. The latter illustrate the electrochemical imaging aspects of the device using two technologically relevant examples

Shape and Charge: Faraday's Ice Pail Experiment Revisited

Electrically insulating objects gain a net electrical charge when brought in and out of contact. This phenomenon, known as triboelectrification, is very common and familiar to many of us from a car static zap, to the danger of ignition for hydrocarbons flowing through poorly grounded pipes, to the transfer of inks in a xerographic device. Despite our familiarity with triboelectrification, we still do not have a complete chemical picture of its origin,(1−4) and the exact mechanism by which objects that do not conduct electricity gain an electric charge remains a long-standing scientific puzzle.(4−6) In this issue of ACS Central Science, Soh and co-workers explore another aspect of this phenomenon: the relationship between static charge and the shape of the objects.(7

Oxidative Damage during the Operation of Si(211)-Based Triboelectric Nanogenerators

Triboelectric nanogenerators (TENGs) based on sliding metal–semiconductor junctions are an emerging technology that can efficiently convert mechanical into electrical energy. These miniature autonomous power sources can output large direct current (DC) densities, but often suffer from limited durability; hence, their practical scope remains uncertain. Herein, through a combination of conductive atomic force microscopy (C-AFM) and photocurrent decay (PCM) experiments, we explored the underlying cause of surface wear during the operation of DC-TENGs. Using monolayer-functionalized Si(211) surfaces as the model system, we demonstrate the extent to which surface damage develops during TENG operation. We reveal that the introduction of surface defects (oxide growth) during TENG operation is not caused by the passage of the rather large current densities (average output of ~2 × 106 A/m2); it is instead mainly caused by the large pressure (~GPa) required for the sliding Schottky diode to output a measurable zero-bias current. We also discovered that the drop in output during operation occurs with a delay in the friction/pressure event, which partially explains why such deterioration of DC-TENG performance is often underestimated or not reported

Bubbles pinned on electrodes: Friends or foes of aqueous electrochemistry?

Electrochemists and engineers regard adherent gas bubbles as redox-inactive and therefore blocking entities. Adhesion of bubbles at electrodes generally carries an energy penalty. But this is not always the case: bubbles pinned on an electrode surface initiate the oxidation of water-soluble species under conditions where such reactions would normally be considered impossible. Here we critically review the recent literature that is beginning to unveil the novel concept of on-water electrochemistry. Harnessing electrochemical reactivity of the water–gas–electrode interface has the potential to become a game-changer in organic electrosynthesis, accelerating the transition toward a sustainable chemical industry by simplifying the direct integration of renewable electricity into the production of commodity chemicals

Improving the performances of direct-current triboelectric nanogenerators with surface chemistry

Over the past decade, triboelectric nanogenerators (TENGs) – small and portable devices designed to harvest electricity from mechanical vibrations and friction – have matured from a niche theme of electrical engineering research into multidisciplinary research encompassing materials science, physics, and chemistry. Recent advances in both the fundamental understanding and performances of TENGs have been made possible by surface chemistry, electrochemistry, and theoretical chemistry research entering this active and promising field. This short review focuses on the recent developments of direct-current (DC) TENGs, where sliding friction or repetitive contact–separation cycles between the surface of polymers, metals, chemically modified semiconductors, and more recently even by the simple contact of surfaces with water solutions, can output DC suitable to power electronic devices without the need of additional rectification. We critically analyze the role of surface chemistry toward maximizing DC TENG outputs and device longevity. The major current hypotheses about their working mechanism(s) are also discussed

Facet-resolved electrochemistry: From single particles to macroscopic crystals

Optimizing the kinetics and energy requirements of electrochemical reactions is central to the design of redox systems whose function ranges from energy conversion, to chemical catalysis and sensing. This optimization takes often the form of a trial-and-error search for the optimal electrode material. Recent research has revealed pronounced facet-dependent electrical conductivity, redox reactivity and electro-adsorption for a range of technologically relevant semiconductors, including silicon, Cu2O, GaAs, InN, Ag2O, and β-Ga2O3. We analyze selected recent reports, highlighting situations where testing alternative crystal cuts of the same material can be an effective electrode-optimization process. We discuss what is unambiguously known as well as what is emerging but still unclear, such as when and how electrical conductivity and electrochemical rates scale with each other (and when not), or the use of facet-dependent electro-adsorption to direct crystal growth and monolayer deposition. When there are contrasting or counterintuitive views, we explore the assumptions that underlie them

Effect of Chemical Structure on the Electrochemical Cleavage of Alkoxyamines

A test set of 14 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-based alkoxyamines was studied via a combination of cyclic voltammetry and accurate quantum chemistry to assess the effect of substituents on electrochemical cleavage. The experimental oxidation potentials of alkoxyamines falling into the range of 1.1-1.6 V versus Ag/AgCl in acetonitrile, were well reproduced by theory (MAD 0.04 V), with values showing good correlation with the σR Hammett parameters of both the R-group and the OR-group in TEMPO-R. Importantly, most of the studied alkoxyamines underwent oxidative cleavage to form either TEMPO· and R+ or TEMPO+ and R·, with the former favored by electron-donating substituents on R (e.g., 2-oxolane, Ac, CH(CH3)Ph, i-Pr, t-Bu) and the latter by electron withdrawing substituents (Bn, allyl, CH(CH3)C(O)OCH3, C(CH3)2C(O)OCH3, CH(CH3)CN). Where R is not stabilized (e.g., R = CH2C(O)OCH3, Me, Et), fully or almost fully reversible oxidation - without cleavage - was observed, making these species promising candidates for battery applications. Finally, in the case of R = Ph, where N-O cleavage occurred, a phenoxy cation and an aminyl radical were generated. On the basis of these results, TEMPO-based alkoxyamines can provide a variety of electrochemically generated carbon-centered radicals and carbocations for use in synthesis, polymerization, and surface modification

Direct-current output of silicon–organic monolayer–platinum Schottky TENGs: Elusive friction-output relationship

Triboelectric nanogenerators (TENGs) are an emerging energy harvesting technology able to convert ubiquitous mechanical energy into electricity. Friction, static charging and flexoelectricity are all involved in the mechanism underpinning TENG operation, but their relative contribution has remained elusive. Here we used dynamic and static conductive atomic force microscopy (C-AFM) measurements on monolayer-modified silicon crystals to detect evidence of a relationship between friction and zero-bias current, and between pressure and the direction of the putative flexovoltage. We demonstrate that a static electricity-related tribovoltage is probably responsible for a friction excess, and that surprisingly this friction excess is found to be dependent on the doping level and type of the silicon substrate. Such friction excess is however no longer measurable once current is allowed to flow across the junction. This observation points to an electrostatic origin of friction in silicon-based Schottky TENGs, and suggests that the zero external bias DC current is at least in part an electronic flow to neutralize static charges. Further, the sign of the zero-bias current, but not its magnitude, is independent of the semiconductor doping type, which is again suggestive of surface statics being a main contributor to the zero-bias output rather than exclusively a space-charge effect. We also reveal the presence of a junction flexovoltage under pressures common in AFM experiments (GPa), even for negligible lateral friction. In a static Pt–monolayer–n-type Si junction the flexovoltage carries the same sign as the tribovoltage, and can reach such magnitude to overwrite external voltages as high as 2 V. The immediate implication is that the flexovoltage is likely to have i) a strong contribution to the zero-bias output of a n-Si Schottky TENG, ii) a negative effect on the output of a p-Si TENG, and iii) its detection can be straightforward, as we discovered that flexoelectricity manifests as an “inverted diode”: a n-type Si–platinum diode with negligible current even when the n-type material is negatively biased as long as the “static” diode remains under a large normal pressure

Mechanism of Oxidative Alkoxyamine Cleavage: The Surprising Role of the Solvent and Supporting Electrolyte

In this work, we show that the nature of the supporting electrolyte and solvent can dramatically alter the outcome of the electrochemically mediated cleavage of alkoxyamines. A combination of cyclic voltammetry experiments and quantum chemistry is used to study the oxidation behavior of TEMPO-i-Pr under different conditions. In dichloromethane, using a noncoordinating electrolyte (TBAPF6), TEMPO-i-Pr undergoes reversible oxidation, which indicates that the intermediate radical cation is stable toward mesolytic fragmentation. In contrast, in tetrahydrofuran with the same electrolyte, oxidized TEMPO-i-Pr undergoes a rapid and irreversible fragmentation. In nitromethane and acetonitrile, partially irreversible oxidation is observed, indicating that fragmentation is much slower. Likewise, alkoxyamine oxidation in the presence of more strongly coordinating supporting electrolyte anions (BF4-, ClO4-, OTf-, HSO4-, NO3-) is also irreversible. These observations can be explained in terms of solvent- or electrolyte-mediated SN2 pathways and indicate that oxidative alkoxyamine cleavage can be "activated" by introducing coordinating solvents or electrolytes or be "inhibited" through the use of noncoordinating solvents and electrolytes

Single-molecule electrical contacts on silicon electrodes under ambient conditions

The ultimate goal in molecular electronics is to use individual molecules as the active electronic component of a real-world sturdy device. For this concept to become reality, it will require the field of single-molecule electronics to shift towards the semiconducting platform of the current microelectronics industry. Here, we report silicon-based single-molecule contacts that are mechanically and electrically stable under ambient conditions. The single-molecule contacts are prepared on silicon electrodes using the scanning tunnelling microscopy break-junction approach using a top metallic probe. The molecular wires show remarkable current–voltage reproducibility, as compared to an open silicon/nano-gap/metal junction, with current rectification ratios exceeding 4,000 when a low-doped silicon is used. The extension of the single-molecule junction approach to a silicon substrate contributes to the next level of miniaturization of electronic components and it is anticipated it will pave the way to a new class of robust single-molecule circuits