• Journal of Electrochemical Science and Technology
• /
• v.15 no.2
• /
• pp.207-219
• /
• 2024

Metal-N-C (MNC) catalysts have been anticipated as promising candidates for oxygen reduction reaction (ORR) to achieve low-cost polymer electrolyte membrane fuel cells. The structure of the M-N_x moiety enabled a high catalytic activity that was not observed in previously reported transition metal nanoparticle-based catalysts. Despite progress in non-precious metal catalysts, the low density of active sites of MNCs, which resulted in lower single-cell performance than Pt/C, needs to be resolved for practical application. This review focused on the recent studies and methodologies aimed to overcome these limitations and develop an inexpensive catalyst with excellent activity and durability in an alkaline environment. It included the possibility of non-precious metals as active materials for ORR catalysts, starting from Co phthalocyanine as ORR catalyst and the development of methodologies (e.g., metal-coordinated N-containing polymers, metal-organic frameworks) to form active sites, M-N_x moieties. Thereafter, the motivation, procedures, and progress of the latest research on the design of catalyst morphology for improved mass transport ability and active site engineering that allowed the promoted ORR kinetics were discussed.

• Korean Chemical Engineering Research
• /
• v.60 no.1
• /
• pp.151-158
• /
• 2022

Iron and nitrogen coordinated carbon catalyst (Fe-N-C) is the most promising non-precious metal catalyst (NPMC) studied to alternate the Pt-group oxygen reduction reaction (ORR) catalyst. In this work, Fe/N/C type catalysts are prepared by four different nitrogen precursors; N, N, N', N'-tetramethylethylenediamine (TMEDA), 1,2-ethylenediamine (EDA), m-dicyanobenzene (DCB), dicyandiamide (DCDA) which can chelate a transition metal; In addition, the catalysts conducted the pyrolysis process at four different temperatures of 700, 800, 900, 1000 ℃ to investigate the ORR activities depend on pyrolysis temperature and to find an appropriate temperature. The characterizations of catalysts were investigated by scanning electron microscope-energy dispersive X-ray spectrometer (SEM-EDS), X-ray diffraction (XRD), and element analysis (EA). The electrocatalytic activity was measured by ORR polarization, also the electron transfer number was calculated from the slope of the K-L plot. The FeNC-EDA-800 which were prepared at pyrolysis temperature of 800 ℃ with EDA showed better ORR activity than the other catalysts.

• Journal of the Korean Electrochemical Society
• /
• v.23 no.4
• /
• pp.90-96
• /
• 2020

Polymer electrolyte membrane fuel cells, which convert the chemical reaction energy of hydrogen into electric power directly, are a type of eco-friendly power for future vehicles. Due to the sluggish oxygen reduction reaction and costly Pt catalyst in the cathode, the research related to the replacement of Pt-based catalysts has been vitally carried out. In this case, however, the performance is significantly different from each other and a variety of factors have existed. In this review paper, we rearrange and summarize relevant papers published within 5 years approximately. The selection of precursors, synthesis method, and co-catalyst are represented as a core factor, while the necessity of research for the further enhancement of activity may be raised. It can be anticipated to contribute to the replacement of precious metal catalysts in the various fields of study. The final objective of the future research is depicted in detail.

• 한국태양에너지학회:학술대회논문집
• /
• 2012.03a
• /
• pp.406-409
• /
• 2012

Recently, enormous research efforts have been focused on the development of non-precious catalysts to replace Pt for electrocatalytic oxygen reduction reaction (ORR), and to reduce the cost of proton exchange membrane fuel cells (PEMFCs). In recent years, heteroatom (N, B, and P) doped carbon nanostructures have been received enormous importance as a non-precious electrode materials for oxygen reduction. Doping of foreign atom into carbon is able to modify electronic properties of carbon materials. In this study, nitrogen and boron doped carbon nanostructures were synthesized by using a facile and cost-effective thermal annealing route and prepared nanostructures were used as a non-precious electrocatalysts for the ORR in alkaline electrolyte. The nitrogen doped carbon nanocapsules (NCNCs) exhibited higher activity than that of a commercial Pt/C catalyst, excellent stability and resistance to methanol oxidation. The boron-doped carbon nanostructure (BC) prepared at $900^{\circ}C$ showed higher ORR activity than BCs prepared lower temperature (800, $700^{\circ}C$). The heteroatom doped carbon nanomaterials could be promising candidates as a metal-free catalysts for ORR in the PEMFCs.

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

• Journal of the Korean Electrochemical Society
• /
• v.16 no.1
• /
• pp.52-58
• /
• 2013

In order to overcome the cost issue for commercialization of polymer electrolyte membrane fuel cell (PEMFC), this research was conducted for replacing platinum cathode catalyst with non-precious metal catalyst. The non-precious metal catalyst (Co-PANI-C) was synthesized by the simple reduction method with polyaniline (PANI), carbon black, and cobalt precursor without any heat treatment. Characterization of new Co-PANI-C composite catalysts was done by the measurement of X-ray diffraction (XRD) and thermogravimetric analysis (TGA) for structure analysis and performed by rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) for electrochemical analysis. As a result, Co-PANI-C catalyst showed 60 mV lower on-set potential for oxygen reduction reaction (ORR) than Pt/C catalyst, but the overall reduction current of Co-PANI-C catalysts by ORR was still smaller than that of Pt/C. In addition, the ORR behavior of Co-PANI-C catalysts depending on the rotation speed of electrode and the stability of Co-PANI-C catalyst under potential cycling and the performance of fuel cell conditions are also discussed.

• Journal of Ceramic Processing Research
• /
• v.19 no.6
• /
• pp.499-503
• /
• 2018

In this paper, cobalt embedded in nitrogen and sulfur co-doped carbon nanotubes (CoNSTs) were synthesized for oxygen reduction reaction (ORR) catalysts. The CoNSTs were prepared through a facile heat treatment method without any templates. Different amounts of the metal salt were employed to examine the physicochemical and electrochemical properties of the CoNSTs. The CoNSTs showed the bamboo-like tube morphology with the encased Co nanoparticles in the tubes. Through the x-ray photoelectron spectroscopy analysis, the catalysts exhibited different chemical states of the nitrogen and sulfur species. As a result, the CoNST performed high activity toward the ORR in an acidic condition with the onset potential of 0.863 V (vs. reversible hydrogen electrode). It was clearly demonstrated from the electrochemical characterizations that the quality of the nitrogen and sulfur species significantly influences the ORR activity rather than the total amount of the dopants.

• Journal of Electrochemical Science and Technology
• /
• v.12 no.1
• /
• pp.137-145
• /
• 2021

Among the non-precious metal catalysts, iron-nitrogen doped carbon (Fe-N/C) catalysts have been recognized as the most promising candidates for an alternative to Pt-based catalysts for the oxygen reduction reaction (ORR) under alkaline and acidic conditions. In this study, the nano replication method using mesoporous silica, which features tunable primary particle sizes and shape, is employed to prepare the mesoporous Fe-N/C catalysts with different shapes. Platelet SBA-15, irregular KIT-6, and spherical silica particle (SSP) were selected as a template to generate three different kinds of shapes of the mesoporous Fe-N/C catalyst. Physicochemical properties of mesoporous Fe-N/C catalysts are characterized by using small-angle X-ray diffraction, nitrogen adsorption-desorption isotherms, and scanning electron microscopy images. According to the electrochemical evaluation, there is no morphological preference of mesoporous Fe-N/C catalysts toward the ORR activity with half-cell configuration under alkaline electrolyte. By implementing X-ray photoelectron spectroscopy analysis of Fe and N atoms in the mesoporous Fe-N/C catalysts, it is possible to verify that the activity towards ORR highly depends on the portions of "Fe-N" species in the catalysts regardless of the shape of catalysts. It was suggested that active site distribution in the Fe-N/C is one important factor towards ORR activity.

• Applied Chemistry
• /
• v.15 no.1
• /
• pp.81-84
• /
• 2011

Platinum catalyst activity and stability is excellent in terms of fuel cells as a catalyst here. Although it is widely used, to compensate for the high price issue non-precious fuel cell catalysts are being developed. In this study, Co/PANi/CNT composite and non-precious as a catalyst for oxygen reduction was applied. Polyaniline on the interaction between cobalt and the oxygen reduction reaction and the structural characteristics observed in the impact and heat treatment was carried out according to the improved catalytic performance. Potential range is oxygen reduction reaction 0.55 V to 0.78 V(vs. NHE) after pyrolysis. Through this study, Co /PANi/CNT composites as a potential catalyst for fuel cells were non-precious.

• Journal of the Korean Electrochemical Society
• /
• v.26 no.4
• /
• pp.64-70
• /
• 2023

Global warming is getting worse since a dramatic increase in greenhouse gas emissions recently. As a result, the necessity and implementation of carbon neutrality is required more urgently. To do this, among various new and renewable energies, attention in hydrogen arises. Hydrogen as a carbon-free power source is an abundant resource on Earth and is eco-friendly. Eventually, perfectly eco-friendly hydrogen can be obtained through electrolysis of water. However, the catalyst used in the oxygen evolution reaction is rare and expensive, and has a durability issue. Consequently, the development of a non-precious metal catalyst is necessary. In this review paper, we summarize and introduce Co- and Mo- based catalysts among recently announced oxygen evolution catalysts. This will help understand the design of catalyst to increase the activity and durability of non-precious metal catalysts.