• Journal of Electrochemical Science and Technology
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• v.14 no.2
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• pp.105-119
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• 2023

The electrochemical chlorine evolution reaction (CER) is an important electrochemical reaction and has been widely used in chlor-alkali electrolysis, on-site generation of ClO^-, and Cl₂-mediated electrosynthesis. Although precious metal-based mixed metal oxides (MMOs) have been used as CER catalysts for more than half a century, they intrinsically suffer from a selectivity problem between the CER and parasitic oxygen evolution reaction (OER). Hence, the design of selective CER electrocatalysts is critically important. In this review, we provide an overview of the fundamental issues related to the electrocatalysis of the CER and design strategies for selective CER electrocatalysts. We present experimental and theoretical methods for assessing the active sites of MMO catalysts and the origin of the scaling relationship between the CER and the OER. We discuss kinetic analysis methods to understand the kinetics and mechanisms of CER. Next, we summarize the design strategies for new CER electrocatalysts that can enhance the reactivity of MMO-based catalysts and overcome their scaling relationship, which include the doping of MMO catalysts with foreign metals and the development of non-precious metal-based catalysts and atomically dispersed metal catalysts.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.151-151
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• 2012

A new plasma process, i.e., the combination of PIII&D and HIPIMS, was developed to implant non-gaseous ions into materials surface. HIPIMS is a special mode of operation of pulsed-DC magnetron sputtering, in which high pulsed DC power exceeding ~1 kW/$cm^2$ of its peak power density is applied to the magnetron sputtering target while the average power density remains manageable to the cooling capacity of the equipment by using a very small duty ratio of operation. Due to the high peak power density applied to the sputtering target, a large fraction of sputtered atoms is ionized. If the negative high voltage pulse applied to the sample stage in PIII&D system is synchronized with the pulsed plasma of sputtered target material by HIPIMS operation, the implantation of non-gaseous ions can be successfully accomplished. The new process has great advantage that thin film deposition and non-gaseous ion implantation along with in-situ film modification can be achieved in a single plasma chamber. Even broader application areas of PIII&D technology are believed to be envisaged by this newly developed process. In one application of non-gaseous plasma immersion ion implantation, Ge ions were implanted into SiO2 thin film at 60 keV to form Ge quantum dots embedded in SiO2 dielectric material. The crystalline Ge quantum dots were shown to be 5~10 nm in size and well dispersed in SiO2 matrix. In another application, Ag ions were implanted into SS-304 substrate to endow the anti-microbial property of the surface. Yet another bio-application was Mg ion implantation into Ti to improve its osteointegration property for bone implants. Catalyst is another promising application field of nongaseous plasma immersion ion implantation because ion implantation results in atomically dispersed catalytic agents with high surface to volume ratio. Pt ions were implanted into the surface of Al2O3 catalytic supporter and its H2 generation property was measured for DME reforming catalyst. In this talk, a newly developed, non-gaseous plasma immersion ion implantation technique and its applications would be shown and discussed.

• Applied Chemistry for Engineering
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• v.5 no.2
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• pp.285-294
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• 1994

Some supported gold catalysts were prepared by impregnation and coprecipitation methods. Effect of gold addition and active sloe formation were studied by investigating particle sizes of gold, amounts of oxygen adsorbed, adsorption properties of CO and NO, and reduction and oxidation properties, etc.. The gold particles of the catalyst by impregnation were irregular and very large as 30~100 nm, but those by coprecipitation were uniform and ultra-fine as about 4 nm. On $Au/Al_2O_3$ catalyst, the addition of gold to inactive $Al_2O_3$ caused the decomposition of $N_2O$, and CO was not irreversibly adsorbed while $O_2$ was atomically and irreversibly adsorbed. The adsorption sites of oxygen were attributed to the active sites which were restricted to the circumference of hemispherical gold particle-support interface rather than all atoms on the surface of gold particle. Also, CO was reversibly and irreversibly adsorbed on $Al_2O_3$ at low temperature, and the addition of gold weakened both reversible and irreversible adsorptions. The affinity for CO on $Au/Co_3O_4$ catalyst decreased conspicuously compared to $Co_3O_4$. The effect of gold addition did not appear in reduction step but did remarkably in reoxidation step; the added gold promoted the reoxidation of the reduced cobalt atoms.