Zidong Wei

Understanding the High Activity of Fe–N–C Electrocatalysts in Oxygen Reduction: Fe/Fe3C Nanoparticles Boost the Activity of Fe–Nx

Understanding the origin of high activity of Fe-N-C electrocatalysts in oxygen reduction reaction (ORR) is critical but still challenging for developing efficient sustainable nonprecious metal catalysts in fuel cells and metal-air batteries. Herein, we developed a new highly active Fe-N-C ORR catalyst containing Fe-N(x) coordination sites and Fe/Fe3C nanocrystals (Fe@C-FeNC), and revealed the origin of its activity by intensively investigating the composition and the structure of the catalyst and their correlations with the electrochemical performance. The detailed analyses unambiguously confirmed the coexistence of Fe/Fe3C nanocrystals and Fe-N(x) in the best catalyst. A series of designed experiments disclosed that (1) N-doped carbon substrate, Fe/Fe3C nanocrystals or Fe-N(x) themselves did not deliver the high activity; (2) the catalysts with both Fe/Fe3C nanocrystals and Fe-N(x) exhibited the high activity; (3) the higher content of Fe-N(x) gave the higher activity; (4) the removal of Fe/Fe3C nanocrystals severely degraded the activity; (5) the blocking of Fe-N(x) downgraded the activity and the recovery of the blocked Fe-N(x) recovered the activity. These facts supported that the high ORR activity of the Fe@C-FeNC electrocatalysts should be ascribed to that Fe/Fe3C nanocrystals boost the activity of Fe-N(x). The coexistence of high content of Fe-N(x) and sufficient metallic iron nanoparticles is essential for the high ORR activity. DFT calculation corroborated this conclusion by indicating that the interaction between metallic iron and Fe-N4 coordination structure favored the adsorption of oxygen molecule. These new findings open an avenue for the rational design and bottom-up synthesis of low-cost highly active ORR electrocatalysts.

Space‐Confinement‐Induced Synthesis of Pyridinic‐ and Pyrrolic‐Nitrogen‐Doped Graphene for the Catalysis of Oxygen Reduction

The development of high-performance and low-cost catalytic materials for the oxygen reduction reaction (ORR) has been a major challenge for the large-scale application of fuel cells. Currently, platinum and platinum-based alloys are the most efficient ORR catalysts in fuel-cell cathodes; however, they cannot meet the demand for the widespread commercialization of fuel cells because of the scarcity of platinum. Thus, the ongoing search for platinum-free catalysts for the ORR has attracted much attention. Graphene, single-layer sheets of sp-hybridized carbon atoms, has attracted tremendous attention and research interest. The abundance of free-flowing p electrons in carbon materials composed of sp-hybridized carbon atoms makes these materials potential catalysts for reactions that require electrons, such as the ORR. However, these p electrons are too inert to be used directly in the ORR. In N-doped electron-rich carbon nanostructures, carbon p electrons have been shown to be activated through conjugation with lone-pair electrons from N dopants; thus, O2 molecules are reduced on the positively charged C atoms that neighbor N atoms. Recently, Hu and co-workers found that as long as the electroneutrality of the sp-hybridized carbon atoms is broken and charged sites that favor O2 adsorption are created, these materials will be transformed into active metal-free ORR electrocatalysts regardless of whether the dopants are electron-rich (e.g., N) or electrondeficient (e.g., B). Nitrogen-doped carbon (NC) materials are considered to be promising catalysts because of their acceptable ORR activity, low cost, good durability, and environmental friendliness. However, their ORR activity is less competitive, especially in acidic media. Relative to commercial Pt/C, the difference in the half-wave potential for ORR is within 25 mV in alkaline electrolytes but is greater than 200 mV in acidic electrolytes. The activity of NC materials can be enhanced through efficient N doping with sufficient active species that favor ORR and through an increase in electrical conductivity. The annealing of graphitized carbon materials, such as carbon nanotubes and microporous carbon black, in NH3 leads to insufficient substitution of nitrogen because of the well-ordered structure of the host materials. Alternatively, the direct pyrolysis of nitrogen-containing hydrocarbons or polymers produces NC materials with good incorporation of nitrogen. However, suitable pyrolysis temperatures are difficult to pinpoint; without optimization, temperatures that are excessively low or excessively high lead to low electronic conductivity or a remarkable loss of active N species, respectively. Recently, mesoporous-alumina-assisted and silica-template-assisted nitrogen incorporation, which can preserve a high content of N in synthesized NC materials, have been reported. However the activities of the resulting NC materials in the ORR were still significantly lower than that of Pt/C, even when the N content was as high as 10.7 atm%. Among three types of N atoms, that is, pyridinic, pyrrolic, and quaternary N, only the pyridinic and pyrrolic forms, which have planar structures, have been proven to be active in the ORR. In contrast, quaternary N atoms, which possess a 3D structure, are not active in the ORR. The low electrical conductivity of NC materials with quaternary N atoms results from the interruption of their p–p conjugation by the 3D structure and is thought to be predominantly responsible for the poor catalysis. Therefore, the synthesis of NC materials with more planar pyridinic and pyrrolic N atoms and fewer quaternary N atoms is important for the preparation of ORR-active catalysts. Herein, we present a novel strategy for the selective synthesis of pyridinicand pyrrolic-nitrogen-doped graphene (NG) by the use of layered montmorillonite (MMT) as a quasi-closed flat nanoreactor, which is open only along the perimeter to enable the entrance of aniline (AN) monomer molecules. The flat MMT nanoreactor, which is less than 1 nm thick, extensively constrains the formation of quaternary N because of its 3D structure but facilitates the formation of pyridinic and pyrrolic N. Nitrogen is well-known to be incorporated into quaternary N in tetrahedral sp hybridization but incorporated into pyridinic and pyrrolic N in planar sp hybridization. The confinement effect of MMT ensures that N is incorporated into the structure and that the graphitization is successful without significant loss of N species. Furthermore, planar pyridinic and pyrrolic N can be [*] Dr. W. Ding, Prof. Z.-D. Wei, Dr. S.-G. Chen, Dr. X.-Q. Qi, Dr. T. Yang, Dr. S. F. Alvi, Dr. L. Li The State Key Laboratory of Power Transmission Equipment and System Security and New Technology, College of Chemistry and Chemical Engineering, Chongqing University Shapingba 174, Chongqing (China) E-mail: zdwei@cqu.edu.cn

Nanostructured Polyaniline-Decorated Pt/C@PANI Core–Shell Catalyst with Enhanced Durability and Activity

We have designed and synthesized a polyaniline (PANI)-decorated Pt/C@PANI core-shell catalyst that shows enhanced catalyst activity and durability compared with nondecorated Pt/C. The experimental results demonstrate that the activity for the oxygen reduction reaction strongly depends on the thickness of the PANI shell and that the greatest enhancement in catalytic properties occurs at a thickness of 5 nm, followed by 2.5, 0, and 14 nm. Pt/C@PANI also demonstrates significantly improved stability compared with that of the unmodified Pt/C catalyst. The high activity and stability of the Pt/C@PANI catalyst is ascribed to its novel PANI-decorated core-shell structure, which induces both electron delocalization between the Pt d orbitals and the PANI π-conjugated ligand and electron transfer from Pt to PANI. The stable PANI shell also protects the carbon support from direct exposure to the corrosive environment.

Phosphorus-doped graphene nanosheets as efficient metal-free oxygen reduction electrocatalysts

Metal-free phosphorus-doped graphene nanosheets (P-TRG) with large surface area (496.67 m2 g−1) and relatively high P-doping level (1.16 at.%) were successfully prepared by thermal annealing a homogenous mixture of graphene oxide and 1-butyl-3-methlyimidazolium hexafluorophosphate under argon atmosphere. It was found that the P atoms were substitutionally incorporated into the carbon framework and were partially oxidized, which created new active sites for the oxygen reduction reaction (ORR). Accordingly, the ORR catalytic performance of the P-doped graphene was demonstrated to be better than or at least comparable to that of the benchmark Pt/C catalyst.

An extraordinarily stable catalyst: Pt NPs supported on two-dimensional Ti3C2X2 (X = OH, F) nanosheets for oxygen reduction reaction

High dispersion Pt nanoparticles supported on 2D Ti3C2X2 (X = OH, F) nanosheets are presented and electro-chemical measurements confirm that the Pt/Ti3C2X2 catalyst shows enhanced durability and improved ORR activity compared with the commercial Pt/C catalyst.

A one-step, cost-effective green method to in situ fabricate Ni(OH)2 hexagonal platelets on Ni foam as binder-free supercapacitor electrode materials

Nickel hydroxide (Ni(OH)2) is considered to be a promising alternative to the expensive and toxic RuO2 electrode material for high-performance supercapacitors; however, the fabrication method and electrochemical performance of suitable Ni(OH)2 structures are unsatisfactory. In the present work, a facile, cost-effective green method is developed to in situ fabricate Ni(OH)2 hexagonal platelets on Ni foam as a binder-free supercapacitor electrode with high performance. The Ni(OH)2 hexagonal platelets are self-grown on three-dimensional (3D) Ni foam by a one-step hydrothermal treatment of Ni foam in a 15 wt% H2O2 aqueous solution without the use of nickel salts, acids, bases, or post-treatments. The as-prepared Ni(OH)2 hexagonal platelets-Ni foam (HNF) electrode can be used directly as a supercapacitor electrode material, thereby avoiding the need for binders and conducting agents. The Ni(OH)2 hexagonal platelets demonstrate high capacitance (2534 F g−1 at a scan rate of 1 mV s−1) and excellent cycling stability (97% capacitance retention after 2000 cycles at a scan rate of 50 mV s−1). The fabrication method developed here has the significant advantage of low-cost, facile, green, and additive-free processing, and it is therefore a promising route for preparing self-supported metal (hydr)oxide electrodes for high-performance supercapacitors and other energy-storage devices.

Ni-doped Mo2C nanowires supported on Ni foam as a binder-free electrode for enhancing the hydrogen evolution performance

In this study, an inexpensive electrocatalyst, Ni-doped Mo2C nanowires, were grown directly on Ni foam via a hydrothermal reaction combined with a carburization process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and linear scanning voltammetry (LSV) were used to scrutinize the catalysts and their electrochemical performance. The results showed that the designed NiMo2C/NF catalyst displays enhanced catalytic activity toward hydrogen production with a low onset overpotential of 21 mV. For driving a cathodic current density of 100 mA cm−2, it only needs an overpotential of 150 mV. Such excellent performance of NiMo2C/NF could be ascribed to the high intrinsic activity from a synergistic function of Ni and Mo2C, as well as to the exposure of more Ni-doped Mo2C sites provided by the high aspect ratio of a one-dimensional (1D) structure and rich surface area.

Confining Iron Carbide Nanocrystals inside CNx@CNT toward an Efficient Electrocatalyst for Oxygen Reduction Reaction

The development of low-cost electrocatalysts with comparable activity for oxygen reduction reaction (ORR) to substitute platinum-based catalysts is imperative but still challenging for the commercialization of fuel cells. Herein, we reported a strategy to effectively confine iron carbide nanocrystals in N-doped carbon coated on carbon nanotubes (CNx@CNT), which prevented the agglomeration of iron carbide during pyrolysis and thus provided the sufficient highly active catalytic sites. Together with the benefit from three-dimensional conductive network of CNT-based core-shell structure for fast electron transfer and rapid mass transfer, the developed nanocatalyst exhibited the significantly enhanced electrocatalytic activity for ORR, as well as high durability and methanol tolerance. Moreover, it was interestingly found that the types of the confined iron compounds appreciably affected the performance of the catalysts, and Fe3C might be most effective on improving ORR activity in this case.

Enhanced dispersion and durability of Pt nanoparticles on a thiolated CNT support

High dispersion Pt nanoparticles supported on surface thiolation functional carbon nanotubes (SH-CNTs) is presented and electrochemical measurements confirm that the Pt/SH-CNTs catalyst shows good durability and excellent ORR activity.

In-situ nitrogen-doped nanoporous carbon nanocables as an efficient metal-free catalyst for oxygen reduction reaction

A new N-doped carbon nanomaterial with nanoporous coaxial nanocable structure was designed for achieving the requirements of high nitrogen content, proper nitrogen bonding state, and sufficient electron and mass transportation for an oxygen reduction reaction (ORR) catalyst. The nanoporous sheaths provided more catalytic sites and allowed oxygen and reactants to easily access them for fast mass transfer, whereas carbon nanotube cores provided a three-dimensional conductive network and guaranteed fast electron transfer. As a result, the designed low-cost catalyst exhibited excellent electrocatalytic performance and is one of the most active metal-free ORR catalyst.