Bio‐inspired iron/sulfur/graphene nanocomposite and its use in the catalysis of the oxygen reduction reaction at room temperature in alkaline media on a glassy carbon electrode

This work demonstrates the performance of a bio‐inspired iron/sulfur/graphene nanocomposite as a non‐platinum electrocatalyst for the oxygen reduction reaction (ORR) in an alkaline medium. The catalyst shows the most positive ORR onset potential (1.1 V vs. RHE) according to its unique structure in the alkaline medium (KOH solution, pH = 13) at low temperature (T = 298 K). The catalyst is evaluated by the rotating‐disk electrode (RDE) method under various rotating speeds (0–2,000 rpm) in the potential range ?0.02–1.18 V vs. a rechargeable hydrogen electrode (RHE). The number of transferred electrons, as one of the most important parameters, is almost constant over a wide range of potentials (0.1–0.8 V), which indicates a more efficient four‐electron pathway from O₂ to H₂O on the FePc‐S‐Gr surface. The mean size of catalyst centers are in the nanoscale (<10 nm). The estimated Tafel slope in the appropriate range is about ?110 mV per decade at low current density, and E_1/2 of FePc‐S‐Gr displays a negative shift of only 7.1 mV after 10,000 cycles.     

Nitrogen‐doped Carbon–CoOx Nanohybrids: A Precious Metal Free Cathode that Exceeds 1.0 W cm−2 Peak Power and 100 h Life in Anion‐Exchange Membrane Fuel Cells

Efficient and durable nonprecious metal electrocatalysts for the oxygen reduction (ORR) are highly desirable for several electrochemical devices, including anion exchange membrane fuel cells (AEMFCs). Here, a 2D planar electrocatalyst with CoO_x embedded in nitrogen‐doped graphitic carbon (N‐C‐CoO_x) was created through the direct pyrolysis of a metal–organic complex with a NaCl template. The N‐C‐CoO_x catalyst showed high ORR activity, indicated by excellent half‐wave (0.84 V vs. RHE) and onset (1.01 V vs. RHE) potentials. This high intrinsic activity was also observed in operating AEMFCs where the kinetic current was 100 mA cm^?2 at 0.85 V. When paired with a radiation‐grafted ETFE powder ionomer, the N‐C‐CoO_x AEMFC cathode was able to achieve extremely high peak power density (1.05 W cm^?2) and mass transport limited current (3 A cm^?2) for a precious metal free electrode. The N‐C‐CoO_x cathode also showed good stability over 100 hours of operation with a voltage decay of only 15 % at 600 mA cm^?2 under H₂/air (CO₂‐free) reacting gas feeds. The N‐C‐CoO_x cathode catalyst was also paired with a very low loading PtRu/C anode catalyst, to create AEMFCs with a total PGM loading of only 0.10 mg_Pt‐Ru cm^?2 capable of achieving 7.4 W mg^?1_PGM as well as supporting a current of 0.7 A cm^?2 at 0.6 V with H₂/air (CO₂ free)—creating a cell that was able to meet the 2019 U.S. Department of Energy initial performance target of 0.6 V at 0.6 A cm^?2 under H₂/air with a PGM loading <0.125 mg cm^?2 with AEMFCs for the first time.     

Integrated Ultrafine Co0.85Se in Carbon Nanofibers: An Efficient and Robust Bifunctional Catalyst for Oxygen Electrocatalysis

Transition-metal selenides are emerging as alternative bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR); however, their activity and stability are still less than desirable. Herein, ultrafine Co_0.85Se nanoparticles encapsulated into carbon nanofibers (CNFs), Co_0.85Se@CNFs, is reported as an integrated bifunctional catalyst for OER and ORR. This catalyst exhibits a low OER potential of 1.58 V vs. reversible hydrogen electrode (RHE) (E_{J=10, OER}) to achieve a current density (J) of 10 mA cm⁻² and a high ORR potential of 0.84 V vs. RHE (E_{J=−1, ORR}) to reach −1 mA cm⁻². Thus, the potential between E_{J=10, OER} and E_{J=−1, ORR} is only 0.74 V, indicating considerable bifunctional activity. The excellent bifunctionality can be attributed to high electronic conduction, abundant electrochemically active sites, and the synergistic effect of Co_0.85Se and CNFs. Furthermore, this Co_0.85Se@CNFs catalyst displays good cycling stability for both OER and ORR. This study paves a new way for the rational design of hybrid catalysts composed of transition-metal selenides and carbon materials for efficiently catalyzing OER and ORR.     

Synergistic Enhancement of Electrocatalytic Activity toward Oxygen Reduction Reaction in Alkaline Electrolytes with Pentabasic (Fe,B, N,S, P)‐Doped Reduced Graphene Oxide

As alternatives to Pt‐based electrocatalysts, the development of nonprecious metal catalysts with high performance in the cathodic oxygen reduction reaction (ORR) is highly desirable for widespread use in fuel cells. Here we report a simple approach for preparing pentabasic (Fe, B, N, S, P)‐doped reduced graphene oxide (rGO) via a two‐step doping method of adding boric acid and ferric chloride to ternary (N, S, P)‐doped rGO (NSPG). Electrochemical investigation of the composites for the ORR revealed that simultaneously doping appropriate amounts of Fe and B into the NSPG produced a synergistic effect that endowed the prepared catalyst with both a positively shifted ORR half‐wave potential and high selectivity for the 4e^? reduction of O₂. The optimized Fe₂B‐NSPG catalyst approached a 4e^? process for the ORR with a half‐wave potential (E_1/2=0.90 V vs. RHE) even 30 mV higher than that of the commercial Pt/C catalyst in alkaline solution. Furthermore, relative to the Pt/C catalyst, the Fe₂B‐NSPG demonstrated superior stability and excellent tolerance of the methanol cross‐over effect. This simple method afforded pentabasic (Fe, B, N, S, P)‐doped rGO as a promising nonprecious metal catalyst used for alkaline fuel cells.     

Boosting ORR Catalytic Activity by Integrating Pyridine‐N Dopants,a High Degree of Graphitization,and Hierarchical Pores into a MOF‐Derived N‐Doped Carbon in a Tandem Synthesis

N‐doped carbon materials represent promising metal‐free electrocatalysts for the oxygen reduction reaction (ORR), the cathode reaction in fuel cells, metal–air batteries, and so on. A challenge for optimizing the ORR catalytic activities of these electrocatalysts is to tune their local structures and chemical compositions in a rational and controlled way that can achieve the synergistic function of each factor. Herein, we report a tandem synthetic strategy that integrates multiple contributing factors into an N‐doped carbon. With an N‐containing MOF (ZIF‐8) as the precursor, carbonization at higher temperatures leads to a higher degree of graphitization. Subsequent NH₃ etching of this highly graphitic carbon enabled the introduction of a higher content of pyridine‐N sites and higher porosity. By optimizing these three factors, the resultant carbon materials displayed ORR activity that was far superior to that of carbon derived from a one‐step pyrolysis. The onset potential of 0.955 V versus a reversible hydrogen electrode (RHE) and the half‐wave potential of 0.835 V versus RHE are among the top ranks of metal‐free ORR catalysts and are comparable to commercial Pt/C (20 wt %) catalysts. Kinetic studies revealed lower H₂O₂ yields, higher electron‐transfer numbers, and lower Tafel slopes for these carbon materials compared with that derived from a one‐step carbonization. These findings verify the effectiveness of this tandem synthetic strategy to enhance the ORR activity of N‐doped carbon materials.     

Sulfur‐Modified Oxygen Vacancies in Iron–Cobalt Oxide Nanosheets: Enabling Extremely High Activity of the Oxygen Evolution Reaction to Achieve the Industrial Water Splitting Benchmark

The oxygen vacancies of defective iron–cobalt oxide (FeCoO_x‐Vo) nanosheets are modified by the homogeneously distributed sulfur (S) atoms. S atoms can not only effectively stabilize oxygen vacancies (Vo), but also form the Co?S coordination with Co active site in the Vo, which can modulate the electronic structure of the active site, enabling FeCoO_x‐Vo‐S to exhibit much superior OER activity. FeCoO_x‐Vo‐S exhibits a mass activity of 2440.0 A g^?1 at 1.5 V vs. RHE in 1.0 m KOH, 25.4 times higher than that of RuO₂. The Tafel slope is as low as 21.0 mV dec^?1, indicative of its excellent charge transfer rate. When FeCoO_x‐Vo‐S (anode catalyst) is paired with the defective CoP₃/Ni₂P (cathode catalyst) for overall water splitting, current densities of as high as 249.0 mA cm^?2 and 406.0 mA cm^?2 at a cell voltage of 2.0 V and 2.3 V, respectively, can be achieved.     

Efficient Oxygen Reduction Reaction (ORR) Catalysts Based on Single Iron Atoms Dispersed on a Hierarchically Structured Porous Carbon Framework

Single Fe atoms dispersed on hierarchically structured porous carbon (SA‐Fe‐HPC) frameworks are prepared by pyrolysis of unsubstituted phthalocyanine/iron phthalocyanine complexes confined within micropores of the porous carbon support. The single‐atom Fe catalysts have a well‐defined atomic dispersion of Fe atoms coordinated by N ligands on the 3D hierarchically porous carbon support. These SA‐Fe‐HPC catalysts are comparable to the commercial Pt/C electrode even in acidic electrolytes for oxygen reduction reaction (ORR) in terms of the ORR activity (E_1/2=0.81 V), but have better long‐term electrochemical stability (7 mV negative shift after 3000 potential cycles) and fuel selectivity. In alkaline media, the SA‐Fe‐HPC catalysts outperform the commercial Pt/C electrode in ORR activity (E_1/2=0.89 V), fuel selectivity, and long‐term stability (1 mV negative shift after 3000 potential cycles). Thus, these nSA‐Fe‐HPCs are promising non‐platinum‐group metal ORR catalysts for fuel‐cell technologies.     

The Direct Electron Transfer of Iron‐containing Metal Organic Frameworks (Mil‐100) and Its Catalysis for the Oxygen Reduction Reaction in Room‐Temperature Alkaline Media on a Glass Carbon Electrode

The most common electrocatalysts for the oxygen reduction reaction (ORR) are platinum‐based ones. This work demonstrates the performance of iron‐containing metal organic frameworks (MOFs) as non‐platinum‐based nano‐electrocatalysts for ORR in an alkaline medium. As a new non‐platinum catalyst to achieve the active sites for the ORR, Mil‐100 (Fe) nanoparticles were used in aqueous KOH by the rotating‐disk electrode method. The main objectives of this study are the investigations on the electron transfer number (n ), Tafel slope, and catalytic performance. The particles size of the obtained powders is in the nanoscale range (approximately 25 nm). The electron transfer number for the ORR on the surface of iron‐containing catalyst is approximately 4, and the Tafel slope of diffusion‐corrected kinetic current density is ~50.7 mV per decade at low overpotential. This work might extend a new non‐precious‐metal catalyst structure for ORR for use in low‐temperature fuel cells.     

Atomically Dispersed FeN2P2 Motif with High Activity and Stability for Oxygen Reduction Reaction Over the Entire pH Range

The past decade has witnessed the great potential of Fe-based single-atom electrocatalysis in catalyzing oxygen reduction reaction (ORR). However, it remains a grand challenge to substantially improve their intrinsic activity and long-term stability in acidic electrolytes. Herein, we report a facile chemical vapor deposition strategy, by which high-density Fe atoms (3.97 wt%) are coordinated with square-planar para-positioned nitrogen and phosphorus atoms in a hierarchical carbon framework. The as-crafted atomically dispersed Fe catalyst (denoted Fe-SA/PNC) manifests an outstanding activity towards ORR over the entire pH range. Specifically, the half-wave potential of 0.92 V, 0.83 V, and 0.86 V vs. reversible hydrogen electrode (RHE) are attained in alkaline, neutral, and acidic electrolytes, respectively, representing the high performance among reported catalysts to date. Furthermore, after 30,000 durability cycles, the Fe-SA/PNC remains to be stable with no visible performance decay when tested in 0.1 M KOH and 0.5 M H₂SO₄, and only a minor negative shift of 40 mV detected in 0.1 M HClO₄, significantly outperforming commercial Pt/C counterpart. The coordination motif of Fe-SA/PNC is validated by density functional theory (DFT) calculations. This work provides atomic-level insight into improving the activity and stability of non-noble metal ORR catalysts, opening up an avenue to craft the desired single-atom electrocatalysts.     

Isolated Single Iron Atoms Anchored on N‐Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

The development of low‐cost, efficient, and stable electrocatalysts for the oxygen reduction reaction (ORR) is desirable but remains a great challenge. Herein, we made a highly reactive and stable isolated single‐atom Fe/N‐doped porous carbon (ISA Fe/CN) catalyst with Fe loading up to 2.16 wt %. The catalyst showed excellent ORR performance with a half‐wave potential (E _1/2) of 0.900 V, which outperformed commercial Pt/C and most non‐precious‐metal catalysts reported to date. Besides exceptionally high kinetic current density (J _k) of 37.83 mV cm⁻² at 0.85 V, it also had a good methanol tolerance and outstanding stability. Experiments demonstrated that maintaining the Fe as isolated atoms and incorporating nitrogen was essential to deliver the high performance. First principle calculations further attributed the high reactivity to the high efficiency of the single Fe atoms in transporting electrons to the adsorbed OH species.     

Red Bean Pod Derived Heterostructure Carbon Decorated with Hollow Mixed Transition Metals as a Bifunctional Catalyst in Zn-Air Batteries

Design and synthesis of low-cost and efficient bifunctional catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in Zn-air batteries are essential and challenging. We report a facile method to synthesize heterostructure carbon consisting of graphitic and amorphous carbon derived from the agricultural waste of red bean pods. The heterostructure carbon possesses a large surface area of 625.5 m² g⁻¹, showing ORR onset potential of 0.89 V vs. RHE and OER overpotential of 470 mV at 5 mA cm⁻². Introducing hollow FeCo nanoparticles and nitrogen dopant improves the bifunctional catalytic activity of the carbon, delivering ORR onset potential of 0.93 V vs. RHE and OER overpotential of 360 mV. Electron energy-loss spectroscopy (EELS) O K-edge map suggests the presence of localized oxygen on the FeCo nanoparticles, suggesting the oxidation of the nanoparticles. Zn-air battery with these carbon-based catalysts exhibits a peak power density as high as 116.2 mW cm⁻² and stable cycling performance over 210 discharge/charge cycles. This work contributes to the advancement of bifunctional oxygen electrocatalysts while converting agricultural waste into value-added material.     

Iridium Anodic Oxidation to Ir(III) and Ir(IV) Hydrous Oxides

Iridium oxide films (IROFs) are known to have an enhanced or the so‐called super‐Nernstian (<59 mV/pH) pH‐sensitivity. The intention in the present study was to find out the reasons of such behavior and also to elucidate the nature of iridium anodic oxidation processes. The methods employed were combined cyclic voltammetry and chronopotentiometry. Iridium layers of 0.1 to 0.2 μm thickness, deposited thermally on titanium or gold‐plated titanium substrates, were used for investigations. IROFs on the surface of working electrodes were formed anodically by applying a constant potential in deaerated and oxygen‐containing solutions of 0.5 M H₂SO₄, 0.1 M KOH and 0.5 M H₃PO₄+KOH. Linear pH‐dependences of the stationary open‐circuit potential with the slopes close to 59 mV/pH were found for iridium electrode oxidized at 0.4 V–0.8 V (RHE) in deaerated and at 0.8 V–1.2 V (RHE) in O₂‐containing solutions. They were attributed to reversible Ir/Ir(OH)₃ and Ir/ IrO₂?nH₂O metal‐oxide electrodes, respectively. It has been suggested that the main current peaks seen in the voltammograms of iridium electrode in acid and alkaline solutions are of different nature. The difference between iridium electrode surface states in acid and alkaline solutions has been presumed to be the main reason of super‐Nernstian pH‐sensitivity of the IROFs. On the basis of the results obtained standard potential of Ir/Ir(OH)₃ electrode and the solubility product of Ir(OH)₃ have been evaluated: =0.78±0.02 V and K_sp=3.3×10^?64.     

Oxygen reduction reaction on the low index planes of palladium electrodes modified with a monolayer of platinum film

Oxygen reduction reaction (ORR) has been studied on the low index planes of Pd modified with a monolayer of Pt (Pt/Pd(hkl)) in 0.1 M HClO₄ with the use of hanging meniscus rotating disk electrode. The activity for ORR on bare Pd(hkl) electrode depends on the surface structure strongly, however, voltammograms of ORR on Pt/Pd(hkl) electrodes do not depend on the crystal orientation. The specific activities of Pt/Pd(hkl) electrodes at 0.90 V (RHE) are higher than that on Pt(1 1 0) which has the highest activity for ORR in the low index planes of Pt. The mass activity on Pt/Pd(hkl) electrode is 7 times as high as a commercial Pt/C catalyst.     

Synergistic Effects between Atomically Dispersed Fe−N−C and C−S−C for the Oxygen Reduction Reaction in Acidic Media

Various advanced catalysts based on sulfur‐doped Fe/N/C materials have recently been designed for the oxygen reduction reaction (ORR); however, the enhanced activity is still controversial and usually attributed to differences in the surface area, improved conductivity, or uncertain synergistic effects. Herein, a sulfur‐doped Fe/N/C catalyst (denoted as Fe/SNC) was obtained by a template‐sacrificing method. The incorporated sulfur gives a thiophene‐like structure (C−S−C), reduces the electron localization around the Fe centers, improves the interaction with oxygenated species, and therefore facilitates the complete 4 e⁻ ORR in acidic solution. Owing to these synergistic effects, the Fe/SNC catalyst exhibits much better ORR activity than the sulfur‐free variant (Fe/NC) in 0.5 m H₂SO₄.     

CoNi nanoparticles anchored inside carbon nanotube networks by transient heating:Low loading and high activity for oxygen reduction and evolution

Transitional metal alloy and compounds have been developed as the low cost and efficient bifunctional electrocatalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).However,a high mass loading of these catalysts is commonly needed to achieve acceptable catalytic performance,which could cause such problems as battery weight gain,mass transport blocking,and catalyst loss.We report herein the preparation of fine CoNi nanoparticles(5-6 nm)anchored inside a nitrogendoped defective carbon nanotube network(CoNi@N-DCNT)by a transient Joule heating method.When utilized as an electrocatalyst for oxygen reduction and evolution in alkaline media,the CoNi@N-DCNT film catalyst with a very low mass loading of 0.06 mg cm^-2 showed excellent bifunctional catalytic performance.For ORR,the onset potential(Eonset)and the half-wave potential(E_1/2)were 0.92 V versus reversible hydrogen electrode(vs.RHE)and 0.83 V(vs.RHE),respectively.For OER,the potential at the current density(J)of 10 mA cm^-2(E₁₀)was 1.53 V,resulting in an overpotential of 300 mV much lower than that of the commercial RuO₂ catalyst(320 mV).The potential gap between E_1/2 and E₁₀ was as small as 0.7 V.Considering the low mass loading,the mass activity at E₁₀ reached at 123.2 A g^-1,much larger than that of the RuO₂ catalyst and literature results of transitional metal-based bifunctional catalysts.Moreover,the CoNi@N-DCNT film catalyst showed very good long-term stability during the ORR and OER test.The excellent bifunctional catalytic performance could be attributed to the synergistic effect of the bimetal alloy.     

Low‐Pt Loaded on a Vanadium Nitride/Graphitic Carbon Composite as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

The high cost of platinum electrocatalysts for the oxygen reduction reaction (ORR) has hindered the commercialization of fuel cells. An effective support can reduce the usage of Pt and improve the reactivity of Pt through synergistic effects. Herein, the vanadium nitride/graphitic carbon (VN/GC) nanocomposites, which act as an enhanced carrier of Pt nanoparticles (NPs) towards ORR, have been synthesized for the first time. In the synthesis, the VN/GC composite could be obtained by introducing VO₃^? and [Fe(CN)₆]^4? ions into the polyacrylic weak‐acid anion‐exchanged resin (PWAR) through an in‐situ anion‐exchanged route, followed by carbonization and a subsequent nitridation process. After loading only 10 % Pt NPs, the resulting Pt‐VN/GC catalyst demonstrates a more positive onset potential (1.01 V), higher mass activity (137.2 mA mg^?1), and better cyclic stability (99 % electrochemical active surface area (ECSA) retention after 2000 cycles) towards ORR than the commercial 20 % Pt/C. Importantly, the Pt‐VN/GC catalyst mainly exhibits a 4 e^?‐transfer mechanism and a low yield of peroxide species, suggesting its potential application as a low‐cost and highly efficient ORR catalyst in fuel cells.     

A Carbon Electrode Functionalized by a Tricopper Cluster Complex: Overcoming Overpotential and Production of Hydrogen Peroxide in the Oxygen Reduction Reaction

A study of the oxygen reduction reaction (ORR) on a screen printed carbon electrode surface mediated by the tricopper cluster complex Cu₃(7‐N‐Etppz(CH₂OH)) dispersed on electrochemically reduced carbon black, where 7‐N‐Etppz(CH₂OH) is the ligand 3,3′‐(6‐(hydroxymethyl)‐1,4‐diazepane‐1,4‐diyl)bis(1‐(4‐ethyl piperazin‐1‐yl)propan‐2‐ol), is described. Onset oxygen reduction potentials of about 0.92 V and about 0.77 V are observed at pH 13 and pH 7 vs. the reversible hydrogen electrode, which are comparable to the best values reported for any synthetic copper complex. Based on half‐wave potentials (E_1/2), the corresponding overpotentials are about 0.42 V and about 0.68 V, respectively. Kinetic studies indicate that the trinuclear copper catalyst can accomplish the 4 e^? reduction of O₂ efficiently and the ORR is accompanied by the production of only small amounts of H₂O₂. The involvement of the copper triad in the O₂ activation process is also verified.     

The Direct Electron Transfer of Iron‐Containing Superoxide Dismutase (Fe‐SOD) and its Catalysis for the Oxygen Reduction Reaction (ORR) in Room Temperature Ionic Liquids (RTILs) on a Gold Electrode

In this work, for the first time, the direct electron transfer of iron‐containing superoxide dismutase (Fe‐SOD) was observed by cyclic voltammetry on a gold (Au) electrode in three RTILs, i.e., 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF₄), 1‐n‐propyl‐3‐methylimidazolium tetrafluoroborate (PMIBF₄) and 1‐n‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIBF₄). And the results demonstrate that when the scan rate was as low as 1 mV/s, a pair of well‐defined quasi‐reversible peaks of Fe‐SOD was presented, while as the potential scan rate was above 10 mV/s, the reduction peak of Fe‐SOD disappeared though its oxidation peak could be clearly observed even as the potential scan rate was up to 400 mV/s, strongly indicating that these CVs we observed were attributable to Fe‐SOD rather than the impurities in RTILs. Its catalysis for oxygen reduction reaction (ORR) was directly verified by the shifting of formal potential, E⁰′, of ORR, to the positive direction though the value of standard rate constant, κ⁰, corresponding to ORR, was not much enhanced. In PMIBF₄, for the multi‐walled carbon nanotubes (MWCNTs)‐modified gold electrode, both the reduction peak current and oxidation peak current for oxygen redox reaction were all dramatically enhanced compared to the case of a bare gold electrode, and the value of κ⁰ was also increased from 3.1 × 10^?3 cm s^?1 for the bare gold electrode, to 17.5 × 10^?3 cm s^?1. Hence, in the presence of Fe‐SOD in RTILs, MWCNTs, showing catalysis for the electron transfer process of ORR, coupled with Fe‐SOD, leading to the shifting of formal potential corresponding to ORR to the positive direction, presented us a satisfactory catalysis for ORR in RTILs. Some reasons available for this catalysis behavior stemming from Fe‐SOD, and MWCNTs as well, for ORR are discussed based on the previously developed proposition.     

Imine Gels Based on Ferrocene and Porphyrin and Their Electrocatalytic Property

A series of porphyrin‐based imine gels have been synthesized via dynamic covalent gelation between 5,10,15,20‐tetra(4‐aminophenyl)‐21H,23H‐porphyrin (H₂TAPP) derivatives and various aldehyde compounds. The porphyrin‐ferrocene imine gels based on MTAPP (M=H₂, Ni²⁺, Co²⁺, Pd²⁺ and Zn²⁺) and ferrocene‐1,1′‐dicarbaldehyde (NA) display efficient HER, OER and ORR activities in alkaline media. Among the gels, CoTAPP‐NA shows an HER current density of 10 mA cm^?2 at low overpotential of 470 mV and small Tafel slope of 110 mV decade^?1 in alkaline media. CoTAPP‐NA also exhibits OER catalytic activity with low overpotential (416 mV for 10 mA cm^?2). CoTAPP‐NA shows ability in overall water splitting in alkaline media. In addition, CoTAPP‐NA exhibits onset potential (E_p) of 0.95 V and half‐wave potential (E_1/2) of 0.84 V in 1.0 mol L^?1 KOH solution for oxygen reduction. Moreover, the gel catalyst shows good stability.     

Highly efficient iron–nitrogen electrocatalyst derived from covalent organic polymer for oxygen reduction

Developing non-precious metal catalyst with high activity, good stability and low cost for electrocatalytic oxygen reduction reaction(ORR) is critical for the wide application of energy conversion system. Here, we developed a cost–effective synthetic strategy via silica assistance to obtain a novel Fe_3C/Fe–N_x–C(named as COPBP-PB-Fe-900-SiO_2) catalyst with effective active sites of Fe–N_xand Fe_3C from the rational design two-dimensional covalent organic polymer(COPBP-PB). The nitrogen-rich COP effectively promotes the formation of active Fe–N_x sites. Additionally, the silica not only can effectively suppress the formation of large Fe-based particles in the catalysts, but also increases the degree of carbonization of the catalyst.The as-prepared COPBP-PB-Fe-900-SiO_2 catalyst exhibits high electrocatalytic activity for ORR with a halfwave potential of 0.85 V vs. reversible hydrogen electrode(RHE), showing comparable activity as compared with the commercial Pt/C catalysts in alkaline media. Moreover, this catalyst also shows a high stability with a nearly constant onset potential and half-wave potential after 10,000 cycles. The present work is highly meaningful for developing ORR electrocatalysts toward wide applications.