Developing nonprecious group metal based electrocatalysts for oxygen reduction is crucial for the commercial success of environmentally friendly energy conversion devices such as fuel cells and ...metal–air batteries. Despite recent progress, elegant bottom-up synthesis of nonprecious electrocatalysts (typically Fe–N x /C) is unavailable due to lack of fundamental understanding of molecular governing factors. Here, we elucidate the mechanistic origin of oxygen reduction on pyrolyzed nonprecious catalysts and identify an activity descriptor based on principles of surface science and coordination chemistry. A linear relationship, depicting the ascending portion of a volcano curve, is established between oxygen-reduction turnover number and the Lewis basicity of graphitic carbon support (accessed via C 1s photoemission spectroscopy). Tuning electron donating/withdrawing capability of the carbon basal plane, conferred upon it by the delocalized π-electrons, (i) causes a downshift of eg-orbitals (d z 2 ) thereby anodically shifting the metal ion’s redox potential and (ii) optimizes the bond strength between the metal ion and adsorbed reaction intermediates thereby maximizing oxygen-reduction activity.
Ni–Fe and Ni–Fe–Co mixed-metal oxide (MMO) films were investigated as electrocatalysts for the oxygen evolution reaction (OER) in 0.1 M KOH. In an effort to optimize MMO morphology, aniline was used ...as a capping agent to produce high-surface-area Ni–Fe–Co films on Raney nickel supports. This catalyst exhibits enhanced mass activity in comparison to the Ni–Fe OER electrocatalysts reported to date. Cyclic voltammetry shows changes in the potential of the Ni2+/3+ transitions in Fe- or Co-containing MMO films. In situ X-ray absorption spectroscopy (XAS) analysis confirms that Fe acts to stabilize Ni in the 2+ oxidation state, while Co facilitates oxidation to the 3+ state. The results of this study support the recent claims that Fe (not Ni) is the OER active site. The OER enhancement of the ternary Ni–Fe–Co catalyst results from two effects: (1) the charge-transfer effects of Co result in the formation of the conductive NiIIIOOH phase at lower overpotential, thus activating the Fe sites which are otherwise inaccessible to electron transfer in the nonconductive NiII(OH)2 host lattice, and (2) XAS analysis shows that the presence of Co effectively “shrinks” the Ni and Fe local geometry, likely resulting in an optimized Fe–OH/OOH bond strength. In addition, analysis of heat-treatment effects indicates that calcination at 400 °C improves the OER activity of Ni–Fe–Co but deactivates Ni–Fe. Annealing studies under argon show that MMO surfaces with a hydrated Ni(OH)2 phase and a crystalline NiO phase exhibit nearly identical OER activities. Finally, the morphology of the MMO catalyst film on Raney Ni support provides excellent catalyst dispersion and should result in high active-site utilization for use in technologically relevant gas-diffusion electrodes.
Transition metals embedded in nitrogen‐doped carbon matrices (denoted as M‐N‐C) are the leading platinum group metal (PGM)‐free electrocatalysts for the oxygen reduction reaction (ORR) in acid, and ...are the most promising candidates for replacing platinum in practical devices such as fuel cells. Two of the long‐standing puzzles in the field are the nature of active sites for the ORR and the reaction mechanism. Poor understanding of the structural and mechanistic basis for the exceptional ORR activity of M‐N‐C electrocatalysts impedes rational design for further improvements. Recently, synchrotron‐based X‐ray absorption spectroscopy (XAS) has been successfully implemented to shed some light on these two issues. In this context, a critical review is given to detail the contribution of XAS to the advancement of the M‐N‐C electrocatalysis to highlight its advantages and limitations.
Synchrotron‐based in situ X‐ray absorption spectroscopy (XAS) is a powerful technique in characterizing platinum group metal (PGM)‐free electrocatalysts under operating conditions. By monitoring the structural and electronic properties of active sites in PGM‐free catalysts as a function of applied potentials, XAS provides new insights into the nature of the active sites and the underlying oxygen reduction reaction mechanisms.
Replacing scarce and expensive platinum (Pt) with metal–nitrogen–carbon (M–N–C) catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells has largely been impeded by the low ...oxygen reduction reaction activity of M–N–C due to low active site density and site utilization. Herein, we overcome these limits by implementing chemical vapour deposition to synthesize Fe–N–C by flowing iron chloride vapour over a Zn–N–C substrate at 750 °C, leading to high-temperature trans-metalation of Zn–N4 sites into Fe–N4 sites. Characterization by multiple techniques shows that all Fe–N4 sites formed via this approach are gas-phase and electrochemically accessible. As a result, the Fe–N–C catalyst has an active site density of 1.92 × 1020 sites per gram with 100% site utilization. This catalyst delivers an unprecedented oxygen reduction reaction activity of 33 mA cm−2 at 0.90 V (iR-corrected; i, current; R, resistance) in a H2–O2 proton exchange membrane fuel cell at 1.0 bar and 80 °C.Replacing platinum with metal–nitrogen–carbon catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells has been impeded by low activity. These limitations have now been overcome by the trans-metalation of Zn–N4 sites into Fe–N4 sites.
Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising ...single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN
C
, CoN
C
and CoN
C
. The O
electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O
-adsorption strength, we conclude that cobalt-based moieties bind O
too weakly for efficient O
reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.
Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in ...close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.
Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR ...catalysts with a wide range of redox potential (E redox) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the E redox of active sites; and the intrinsic activity of active sites with low E redox have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high E redox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low E redox side is limited by either the site-blocking effect and/or intrinsic activity depending on the E redox.
Despite the fundamental and practical significance of the hydrogen evolution and oxidation reactions (HER/HOR), their kinetics in base remain unclear. Herein, we show that the alkaline HER/HOR ...kinetics can be unified by the catalytic roles of the adsorbed hydroxyl (OHad)-water-alkali metal cation (AM+) adducts, on the basis of the observations that enriching the OHad abundance via surface Ni benefits the HER/HOR; increasing the AM+ concentration only promotes the HER, while varying the identity of AM+ affects both HER/HOR. The presence of OHad-(H2O) x -AM+ in the double-layer region facilitates the OHad removal into the bulk, forming OH–-(H2O) x -AM+ as per the hard–soft acid–base theory, thereby selectively promoting the HER. It can be detrimental to the HOR as per the bifunctional mechanism, as the AM+ destabilizes the OHad, which is further supported by the CO oxidation results. This new notion may be important for alkaline electrochemistry.
The commercialization of electrochemical energy conversion and storage devices relies largely upon the development of highly active catalysts based on abundant and inexpensive materials. Despite ...recent achievements in this respect, further progress is hindered by the poor understanding of the nature of active sites and reaction mechanisms. Herein, by characterizing representative iron-based catalysts under reactive conditions, we identify three Fe–N4-like catalytic centers with distinctly different Fe–N switching behaviors (Fe moving toward or away from the N4-plane) during the oxygen reduction reaction (ORR), and show that their ORR activities are essentially governed by the dynamic structure associated with the Fe2+/3+ redox transition, rather than the static structure of the bare sites. Our findings reveal the structural origin of the enhanced catalytic activity of pyrolyzed Fe-based catalysts compared to nonpyrolyzed Fe-macrocycle compounds. More generally, the fundamental insights into the dynamic nature of transition-metal compounds during electron-transfer reactions will potentially guide rational design of these materials for broad applications.
Improving the platinum (Pt) mass activity for the oxygen reduction reaction (ORR) requires optimization of both the specific activity and the electrochemically active surface area (ECSA). We found ...that solution-synthesized Pt/NiO core/shell nanowires can be converted into PtNi alloy nanowires through a thermal annealing process and then transformed into jagged Pt nanowires via electrochemical dealloying. The jagged nanowires exhibit an ECSA of 118 square meters per gram of Pt and a specific activity of 11.5 milliamperes per square centimeter for ORR (at 0.9 volts versus reversible hydrogen electrode), yielding a mass activity of 13.6 amperes per milligram of Pt, nearly double previously reported best values. Reactive molecular dynamics simulations suggest that highly stressed, undercoordinated rhombus-rich surface configurations of the jagged nanowires enhance ORR activity versus more relaxed surfaces.
PDF
