Lianhuan Han

Single molecular catalysis of a redox enzyme on nanoelectrodes

Due to a high turnover coefficient, redox enzymes can serve as current amplifiers which make it possible to explore their catalytic mechanism by electrochemistry at the level of single molecules. On modified nanoelectrodes, the voltammetric behavior of a horseradish peroxidase (HRP) catalyzed hydroperoxide reduction no longer presents a continuous current response, but a staircase current response. Furthermore, single catalytic incidents were captured through a collision mode at a constant potential, from which the turnover number of HRP can be figured out statistically. In addition, the catalytic behavior is dynamic which may be caused by the orientation status of HRP on the surface of the electrode. This modified nanoelectrode methodology provides an electrochemical approach to investigate the single-molecule catalysis of redox enzymes.

Solid-State Redox Solutions: Microfabrication and Electrochemistry

National Science Foundation of China (NSFC)[20973142]; NSFC Innovation Group of Interfacial Electrochmistry[21021002]; National Project 985 of High Education; New Faculty Starting Package of Xiamen University

A Leveling Method Based on Current Feedback Mode of Scanning Electrochemical Microscopy

Substrate leveling is an essential but neglected instrumental technique of scanning electrochemical microscopy (SECM). In this technical note, we provide an effective substrate leveling method based on the current feedback mode of SECM. By using an air-bearing rotary stage as the supporter of an electrolytic cell, the current feedback presents a periodic waveform signal, which can be used to characterize the levelness of the substrate. Tuning the adjusting screws of the tilt stage, substrate leveling can be completed in minutes by observing the decreased current amplitude. The obtained high-quality SECM feedback curves and images prove that this leveling technique is valuable in not only SECM studies but also electrochemical machining.

Electrochemical mechanical micromachining based on confined etchant layer technique

The confined etchant layertechnique (CELT) has been proved an effective electrochemical microfabrication method since its first publication at Faraday Discussions in 1992. Recently, we have developed CELT as an electrochemical mechanical micromachining (ECMM) method by replacing the cutting tool used in conventional mechanical machining with an electrode, which can perform lathing, planing and polishing. Through the coupling between the electrochemically induced chemical etching processes and mechanical motion, ECMM can also obtain a regular surface in one step. Taking advantage of CELT, machining tolerance and surface roughness can reach micro- or nano-meter scale.

Electropolishing of titanium alloy under hydrodynamic mode

Titanium (Ti) alloys are widely used in aerospace industry due to the low density and high corrosion resistance. However, machining and polishing remain great challenges because of the hardness and chemical stability. With a home-made electrochemical machining workstation, cyclic voltammetry is performed at a wide potential range of [0 V, 20 V] to record the details of passivation and depassivation processes under a hydrodynamic mode. The results show that the thickness of viscous layer formed on the alloy surface plays a crucial effect on the electropolishing quality. The technical parameters, including the mechanical motion rate, polishing time and electrode gap, are optimized to achieve a surface roughness less than 1.9 nm, which shows a prospective application in the electrochemical machining of Ti and it alloys.

Combinatorial screening of photoelectrocatalytic system with high signal/noise ratio.

Solar energy is the most abundant nature resource and plays important roles in the sustainable developments of energy and environment. Scanning photoelectrochemical microscopy provides a high-throughput screening method by introducing the combinatorial technique to prepare the substrate with photoelectrochemical catalyst array. However, the signal/noise (S/N) ratio suffers from the background current of indium-tin oxide or fluorine-doped tin oxide itself, including a transient charge-discharge current of electric double layer and a steady-state photocatalytic current. Here we adopt a facile microfabrication method to isolate the substrate area other than the catalyst array from not only the electrolyte solution but also the light illumination. Consequently, the imaging quality has been promoted dramatically due to suppressed background current. This method provides a high S/N ratio screening method, which will be valuable for the high-throughput optimization of the photoelectrocatalytic system.

Synergetic effect enhanced photoelectrocatalysis.

We report synergetic effect enhanced photoelectrocatalysis, in which Fe(3+) and Br(-) are used as the acceptors of photogenerated charges on TiO2 nanoparticles. The kinetic rate of interfacial charge transfer is promoted from (4.0 ± 0.5) × 10(-4) cm s(-1) (TiO2/(O2, Br(-))) to (1.5 ± 0.5) × 10(-3) cm s(-1) (TiO2/(Fe(3+), Br(-))). The synergetic effect provides a valuable approach to the design of photoelectrocatalytic systems.

Nanofabrication of the gold scanning probe for the STM-SECM coupling system with nanoscale spatial resolution

Scanning probe is the key issue for the electrochemical scanning probe techniques (EC-SPM) such as EC-scanning tunnel microscopy (STM), EC-atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM), especially the insulative encapsulation of the nanoelectrode probe for both positioning and electrochemical feedbacks. To solve this problem, we develop a novel fabrication method of the gold nanoelectrodes: firstly, a micropipette with nanomter-sized orifice was prepared as the template by a laser puller; secondly, the inside wall of micropipette apex was blocked by compact and conic Au nano-piece through electroless plating; thirdly, the Au nano-piece was grown by bipolar electroplating and connected with a silver wire as a current collector. The fabricated Au nanoelectrode has very good voltammetric responses for the electrodic processes of both mass transfer and adsorption. The advantage lies in that it is well encapsulated by a thin glass sealing layer with a RG value lowered to 1.3, which makes it qualified in the SECM-STM coupling mode. On one hand, it can serve as STM tip for positioning which ensures the high spatial resolution; on the other hand, it is a high-quality nanoelectrode to explore the local chemical activity of the substrate. The nanofabrication method may promote the SPM techniques to obtain simultaneously the physical and chemical images with nanoscale spatial resolution, which opens a new approach to tip chemistry in electrochemical nanocatalysis and tip-enhanced spectroscopy.

Confined etchant layer technique (CELT) for micromanufacture

Confined etchant layer technique (CELT) is an electro-and/ or photo- chemically induced chemical etching method for micromanufacture originated by our research group, which is distinguished from the LIGA and EFAB. To obtain the micro-/nano- meter precision, there are three strategies of CELT: (1) electro- and/or photo- chemical generation of etchant on the surface of tool; (2) confining the etchant layer to a thickness of micro-/nano- meter; (3) Approaching tool to the workpiece for micromanufacturing. CELT have been proved successful in the micromanufacture on conductive, semiconductive and also insulate workpiece. In this paper, our work on CELT will be reviewed and future research will also be prospected.