Young Jin Sa

Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity.

Ordered mesoporous Co3O4 spinels as stable, bifunctional, noble metal-free oxygen electrocatalysts

We report the use of noble metal-free ordered mesoporous Co3O4 spinels (meso-Co3O4), templated from KIT-6 mesoporous silica, as highly active and stable bifunctional electrocatalysts for both oxygen evolution and reduction reactions (OER and ORR, respectively). The meso-Co3O4 nanostructures showed high activity for OER in an alkaline medium (0.1 M KOH), which makes them comparable to the most active Ir/C catalyst and better than Co3O4 nanoparticles (NPs) and the Pt/C catalyst. Furthermore, meso-Co3O4 exhibited enhanced stability, compared to Co3O4 NPs. The enhanced activity and stability of meso-Co3O4 over Co3O4 NPs could be attributed to its high surface area and structural stability of the gyroid network structure in the meso-Co3O4 catalysts. The meso-Co3O4 nanostructures also showed promising activity for ORR and exhibited a methanol-tolerance superior to the Pt/C catalyst. The total overpotential of meso-Co3O4 for OER (at 10 mA cm−2) and ORR (at −3 mA cm−2) was 1.034 V, which is on a par with noble metal-based catalysts. This work demonstrates that directing metal oxides into mesostructures is a promising means of preparing highly active, stable, bifunctional oxygen electrocatalysts that can potentially replace expensive noble metal-based catalysts. This design strategy can be extended to other reactions relevant to energy conversion and storage applications.

Ordered Mesoporous Carbon Nitrides with Graphitic Frameworks as Metal-Free, Highly Durable, Methanol-Tolerant Oxygen Reduction Catalysts in an Acidic Medium

Developments of high-performance cost-effective electrocatalyts that can replace Pt catalysts have been a central theme in polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). In this direction, nitrogen-doped carbon nanostructures free of metallic components have attracted particular attention. Here we show that directing graphitic carbon nitride frameworks into mesoporous architecture can generate a highly promising metal-free electrocatalyst for an oxygen reduction reaction (ORR) in an acidic medium. The ordered mesoporous carbon nitride (OMCN) was synthesized with a nanocasting strategy using ordered mesoporous silica as a template. A variety of characterizations revealed that the OMCN is constructed with graphitic carbon nitride frameworks and ordered arrays of uniform mesopores. The OMCN showed significantly enhanced electrocatalytic activity for ORR compared to bulk carbon nitride and ordered mesoporous carbon in terms of the current density and onset potential. A high surface area and an increased density of catalytically active nitrogen groups in the OMCN appear to contribute concomitantly to the enhanced performance of the OMCN. Furthermore, the OMCN exhibited superior durability and methanol tolerance to a Pt/C catalyst, suggesting its widespread utilization as an electrocatalyst for PEMFCs and DMFCs.

Carbon Nanotubes/Heteroatom‐Doped Carbon Core–Sheath Nanostructures as Highly Active, Metal‐Free Oxygen Reduction Electrocatalysts for Alkaline Fuel Cells

A facile, scalable route to new nanocomposites that are based on carbon nanotubes/heteroatom-doped carbon (CNT/HDC) core-sheath nanostructures is reported. These nanostructures were prepared by the adsorption of heteroatom-containing ionic liquids on the walls of CNTs, followed by carbonization. The design of the CNT/HDC composite allows for combining the electrical conductivity of the CNTs with the catalytic activity of the heteroatom-containing HDC sheath layers. The CNT/HDC nanostructures are highly active electrocatalysts for the oxygen reduction reaction and displayed one of the best performances among heteroatom-doped nanocarbon catalysts in terms of half-wave potential and kinetic current density. The four-electron selectivity and the exchange current density of the CNT/HDC nanostructures are comparable with those of a Pt/C catalyst, and the CNT/HDC composites were superior to Pt/C in terms of long-term durability and poison tolerance. Furthermore, an alkaline fuel cell that employs a CNT/HDC nanostructure as the cathode catalyst shows very high current and power densities, which sheds light on the practical applicability of these new nanocomposites.

Monolayer-Precision Synthesis of Molybdenum Sulfide Nanoparticles and Their Nanoscale Size Effects in the Hydrogen Evolution Reaction

Metal sulfide-based nanostructured materials have emerged as promising catalysts for hydrogen evolution reaction (HER), and significant progress has been achieved in enhancing their activity and durability for the HER. The understanding of nanoscale size-dependent catalytic activities can suggest critical information regarding catalytic reactivity, providing the scientific basis for the design of advanced catalysts. However, nanoscale size effects in metal sulfide-based HER catalysts have not yet been established fully, due to the synthetic difficulty in precisely size-controlled metal sulfide nanoparticles. Here we report the preparation of molybdenum sulfide (MoS2) nanoparticles with monolayer precision from one to four layers with the nearly constant basal plane size of 5 nm, and their size-dependent catalytic activity in the HER. Using density functional theory (DFT) calculations, we identified the most favorable single-, double-, and triple-layer MoS2 model structures for the HER, and calculated elementary step energetics of the HER over these three model structures. Combining HER activity measurements and the DFT calculation results, we establish that the turnover frequency of MoS2 nanoparticles in the HER increases in a quasi-linear manner with decreased layer numbers. Cobalt-promoted MoS2 nanoparticles also exhibited similar HER activity trend. We attribute the higher HER activity of smaller metal sulfide nanoparticles to the higher degree of oxidation, higher Mo-S coordination number, formation of the 1T phase, and lower activation energy required to overcome transition state. This insight into the nanoscale size-dependent HER activity trend will facilitate the design of advanced HER catalysts as well as other hydrotreating catalysts.

Coordination chemistry of [Co(acac)2] with N-doped graphene: Implications for oxygen reduction reaction reactivity of organometallic Co-O4-N species

Hybridization of organometallic complexes with graphene-based materials can give rise to enhanced catalytic performance. Understanding the chemical structures within hybrid materials is of primary importance. In this work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co(II) (acac)2 ] (acac=acetylacetonate), with N-doped graphene-based materials at room temperature. Experimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt-containing species is coordinated to heterocyclic groups in N-doped graphene as well as to its parental acac ligands. The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to a Pt/C catalyst. Based on the chemical structures and ORR experiments, the catalytically active species is identified as a Co-O4 -N structure.

A transformative route to nanoporous manganese oxides of controlled oxidation states with identical textural properties

Nanoporous nanocrystalline metal oxides with tunable oxidation states are crucial for controlling their catalytic, electronic, and optical properties. However, previous approaches to modulate oxidation states in nanoporous metal oxides commonly lead to the breakdown of the nanoporous structure as well as involve concomitant changes in their morphology, pore size, surface area, and nanocrystalline size. Herein, we present a transformative route to nanoporous metal oxides with various oxidation states using manganese oxides as model systems. Thermal conversion of Mn-based metal–organic frameworks (Mn-MOFs) at controlled temperature and atmosphere yielded a series of nanoporous manganese oxides with continuously tuned oxidation states: MnO, Mn3O4, Mn5O8, and Mn2O3. This transformation enabled the preparation of low-oxidation phase MnO and metastable intermediate phase Mn5O8 with nanoporous architectures, which were previously rarely accessible. Significantly, nanoporous MnO, Mn3O4, and Mn5O8 had a very similar morphology, surface area, and crystalline size. We investigated the electrocatalytic activity of nanoporous manganese oxides for oxygen reduction reaction (ORR) to identify the role of oxidation states, and observed oxidation state-dependent activity and kinetics for the ORR.

Rational design of Pt-Ni-Co ternary alloy nanoframe crystals as highly efficient catalysts toward the alkaline hydrogen evolution reaction

The rational design of highly efficient electrocatalysts for the hydrogen evolution reaction (HER) is of prime importance for establishing renewable and sustainable energy systems. The alkaline HER is particularly challenging as it involves a two-step reaction of water dissociation and hydrogen recombination, for which platinum-based binary catalysts have shown promising activity. In this work, we synthesized high performance platinum-nickel-cobalt alloy nanocatalysts for the alkaline HER through a simple synthetic route. This ternary nanostructure with a Cartesian-coordinate-like hexapod shape could be prepared by a one-step formation of core-dual shell Pt@Ni@Co nanostructures followed by a selective removal of the Ni@Co shell. The cobalt precursor brings about a significant impact on the control of size and shape of the nanostructure. The PtNiCo nanohexapods showed a superior alkaline HER activity to Pt/C and binary PtNi hexapods, with 10 times greater specific activity than Pt/C. In addition, the PtNiCo nanohexapods demonstrated excellent activity and durability for the oxygen reduction reaction in acidic media.

Iridium-Based Multimetallic Nanoframe@Nanoframe Structure: An Efficient and Robust Electrocatalyst toward Oxygen Evolution Reaction

Nanoframe electrocatalysts have attracted great interest due to their inherently high active surface area per a given mass. Although recent progress has enabled the preparation of single nanoframe structures with a variety of morphologies, more complex nanoframe structures such as a double-layered nanoframe have not yet been realized. Herein, we report a rational synthetic strategy for a structurally robust Ir-based multimetallic double-layered nanoframe (DNF) structure, nanoframe@nanoframe. By leveraging the differing kinetics of dual Ir precursors and dual transition metal (Ni and Cu) precursors, a core-shell-type alloy@alloy structure could be generated in a simple one-step synthesis, which was subsequently transformed into a multimetallic IrNiCu DNF with a rhombic dodecahedral morphology via selective etching. The use of single Ir precursor yielded single nanoframe structures, highlighting the importance of employing dual Ir precursors. In addition, the structure of Ir-based nanocrystals could be further controlled to DNF with octahedral morphology and CuNi@Ir core-shell structures via a simple tuning of experimental factors. The IrNiCu DNF exhibited high electrocatalytic activity for oxygen evolution reaction (OER) in acidic media, which is better than Ir/C catalyst. Furthermore, IrNiCu DNF demonstrated excellent durability for OER, which could be attributed to the frame structure that prevents the growth and agglomeration of particles as well as in situ formation of robust rutile IrO2 phase during prolonged operation.

Shape effects of nickel phosphide nanocrystals on hydrogen evolution reaction

The preparation of size- and shape-controlled nanoparticles has enabled the understanding of important nanoscale catalytic phenomena, resulting in the design of advanced catalysts with enhanced activities and selectivities. Metal phosphides have recently emerged as a promising class of non-precious metal catalysts for hydrogen evolution reaction (HER), which is a cornerstone in clean and environmentally benign hydrogen production. Although significant progress has been made in metal phosphide catalysts, the impact of the metal phosphide shape has not yet been explored. Herein, we investigated the shape-dependent electrocatalytic activity of nickel phosphide nanoparticles (Ni2P NPs) for the HER. Spherical Ni2P NPs mainly composed of the Ni2P(001) surface showed higher HER activity than rod-shaped Ni2P NPs with the Ni2P(210) surface in terms of overpotential, Tafel slope, and turnover frequency. The results imply that the Ni2P(001) surface would have preferential interactions with the adsorbent and a lower activation barrier for hydrogen adsorption, promoting the overall rate of HER. This study highlights the importance of morphology control in electrocatalysts to boost catalytic performances.