Calibration and Validation of Simulation Parameters for Maize Straw Based on Discrete Element Method and Genetic Algorithm-Backpropagation.

There is a significant difference between the simulation effect and the actual effect in the design process of maize straw-breaking equipment due to the lack of accurate simulation model parameters in the breaking and processing of maize straw. This article used a combination of physical experiments, virtual simulation, and machine learning to calibrate the simulation parameters of maize straw. A bimodal-distribution discrete element model of maize straw was established based on the intrinsic and contact parameters measured via physical experiments. The significance analysis of the simulation parameters was conducted via the Plackett-Burman experiment. The Poisson ratio, shear modulus, and normal stiffness of the maize straw significantly impacted the peak compression force of the maize straw and steel plate. The steepest-climb test was carried out for the significance parameter, and the relative error between the peak compression force in the simulation test and the peak compression force in the physical test was used as the evaluation index. It was found that the optimal range intervals for the Poisson ratio, shear modulus, and normal stiffness of the maize straw were 0.32-0.36, 1.24 × 108-1.72 × 108 Pa, and 5.9 × 106-6.7 × 106 N/m3, respectively. Using the experimental data of the central composite design as the dataset, a GA-BP neural network prediction model for the peak compression force of maize straw was established, analyzed, and evaluated. The GA-BP prediction model's accuracy was verified via experiments. It was found that the ideal combination of parameters was a Poisson ratio of 0.357, a shear modulus of 1.511 × 108 Pa, and a normal stiffness of 6.285 × 106 N/m3 for the maize straw. The results provide a basis for analyzing the damage mechanism of maize straw during the grinding process.

High-Performance Low-Iridium Catalyst for Water Oxidation: Breaking Long-Ranged Order of IrO2 by Neodymium Doping.

Exploring efficacious low-Ir electrocatalysts for oxygen evolution reaction (OER) is crucial for large-scale application of proton exchange membrane water electrolysis (PEMWE). Herein, an efficient non-precious lanthanide-metal-doped IrO2 electrocatalyst is presented for OER catalysis by doping large-ionic-radius Nd into IrO2 crystal. The doped Nd breaks the long-ranged order structure by triggering the strain effect and thus inducing an atomic rearrangement of Nd─IrO2 involving the forming of Nd─O─Ir bonds along with an increased amount of oxygen vacancies (Ov), giving rise of a long-ranged disorder but a short-ranged order structure. The formed Nd─O─Ir bonds tailor the electronic structure of Ir, leading to a lowered d-band center that weakens intermediates absorption on Ir sites. Moreover, doping Nd triggers Nd─IrO2 to catalyze OER mainly through lattice oxygen mechanism (LOM) by activating lattice oxygen owing to abundant Ov. The optimal catalyst only requires a relatively low overpotential of 263 mV@10 mA cm-2 with a high mass activity of 216.98 A gIr -1 (at 1.53 V) (eightfold of commercial IrO2), and also shows a superior durability at 50 mA cm-2 (20 h) than commercial IrO2 (3 h) due to the oxidation-suppressing effect induced by Nd doping. This work offers insights into designing high-performance low-Ir electrocatalysts for PEMWE application.

Carbonyl-linked cobalt polyphthalocyanines as high-selectivity catalyst for electrochemical CO2 reduction.

One type of carbonyl-linked cobalt polyphthalocyanine (CL-CoPPc) is synthesised as catalysts for use in electrochemical carbon dioxide (CO2) reduction (ECR). Carbonyl linkages can decrease the intermolecular π-π stacking, and serve as intramolecular "gullies" to impede proton transfer and the hydrogen evolution reaction (HER). Therefore, the CL-CoPPc exhibits highly active and selective CO2 reduction to carbon monoxide (CO).

Intriguing H2S Tolerance of the PtRu Alloy for Hydrogen Oxidation Catalysis in PEMFCs: Weakened Pt-S Binding with Slower Adsorption Kinetics.

High quality of hydrogen is the key to the long lifetime of proton-exchange membrane fuel cell (PEMFC) vehicles, while trace H2S impurities in hydrogen significantly affect their durability and fuel expense. Herein, we demonstrate a robust PtRu alloy catalyst with an intriguing H2S tolerance as the PEMFC anode, showing a stronger antipoisoning capability toward hydrogen oxidation reaction compared with the Pt/C anode. The PtRu/C-based single PEMFC shows approximately 14.3% loss of cell voltage after 3 h operation with 1 ppm of H2S in hydrogen, significantly lower than that of Pt/C-based PEMFCs (65%). By adopting PtRu/C as the anode, the H2S limit in hydrogen can be increased to 1.7 times that of the Pt/C anode, assuming that the PEMFC runs for 5000 h, which is conductive for the cost reduction of hydrogen purification. The three-electrode electrochemical test indicates that PtRu/C exhibits a slower adsorption kinetics toward S2- species with poisoning rates of 0.02782, 0.02982, and 0.03682 min-1 at temperatures of 25, 35, and 45 °C, respectively, all lower than those of Pt/C. X-ray absorption fine structure spectra indicate the weakened Pt-S binding for PtRu/C in comparison to Pt/C with a longer Pt-S bond length. Density functional theory calculation analyses reveal that adsorption energy of sulfur on the Pt surface was reduced for PtRu/C, showing 1-10% decrease at different Pt sites for (111), (110), and (100) planes, which is ascribed to the downshifted Pt d-band center caused by the ligand and strain effects due to the introduction of second metallic Ru. This work provides a valuable guide for the development of the H2S-tolerant catalysts for long-term application of PEMFCs.

Construction of three-dimensional cobalt sulfide/multi-heteroatom co-doped porous carbon as an efficient trifunctional electrocatalyst.

Exploring cost-effective non-precious metal electrocatalysts is vital for the large-scale application of clean energy conversion devices (i.e., fuel cells, metal-air batteries and water electrolysers). Herein, we present the construction of a three-dimensional cobalt sulfide/multi-heteroatom co-doped carbon composite as a trifunctional electrocatalyst for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) through one-step sulfidation of zeolitic-imidazolate frameworks (ZIFs) using sulfur powder as a sulfur source. By virtue of the distinct periodic metal-nitrogen coordination structure and the abundant micropores within the ZIF precursor, sub-10 nm Co9S8 nanoparticles (NPs) are homogenously anchored on a Co, S and N multi-heteroatom co-doped carbon framework with a large specific surface area that exposes sufficient reactive sites for these electrocatalytic reactions. The optimized Co9S8/CoNSC exhibits outstanding ORR, OER and HER performance, comparable or even superior to those of commercial Pt/C and RuO2. The small Co9S8 NPs and Co-Nx species embedded in the carbon matrix cooperatively catalyze the OER and ORR, while the HER catalysis is mainly contributed by Co9S8 NPs. Furthermore, the Co9S8/CoNSC shows outstanding anti-poisoning capability towards sulfur species during ORR catalysis with no obvious activity degradation observed in 0.1 M KOH containing 50 µM SO32- species, significantly outperforming commercial Pt/C. The assembled rechargeable Zn-air battery using the Co9S8/CoNSC as a cathode shows a high power density (150 mW cm-2) and the assembled water electrolyzer only requires 1.585 V at a current density of 10 mA cm-2 when using this material as an anode and a cathode. This work provides an effective strategy to design and synthesize efficient, durable and anti-poisoning cobalt chalcogenide-based trifunctional electrocatalysts for the large-scale application of clean energy conversion devices.

Understanding of Correlation between Electronic Properties and Sulfur Tolerance of Pt-Based Catalysts for Hydrogen Oxidation.

Renewable power-derived green hydrogen distributed via natural gas networks is considered one of the viable routes to drive the decarbonization of transportation and distributed power generation, while a trace amount of sulfur impurities is one of the key factors that affect the durability and life cycle expense of proton-exchange membrane fuel cells (PEMFCs) for end users. Herein, we explore the underlying effect of sulfur resistance for Pt-based hydrogen oxidation reaction (HOR) electrocatalysts devoted to high-performance and durable PEMFCs. Two typical electrocatalysts, Pt/C with pure Pt nanoparticles (NPs) and PtCo/C with Pt3Co-alloy-core-Pt-skin NPs, were investigated to demonstrate the structure-property relation for Pt-based electrocatalysts. It was revealed that the PtCo/C demonstrated alleviated sulfur poisoning with the adsorption rate constant reduced by 21.7% compared with Pt/C, and the desorption of the adsorbed sulfur was also more favorable with Pt-S bond decomposition temperature lowered by approximately 25 °C. Characterization indicated that sulfur was predominantly adsorbed in the edge mode for PtCo/C, but in a comparable edge and bridge mode for Pt/C, which caused the strengthened Pt-S binding by the chelation effect for Pt/C. The lowered d-band center of surface Pt for PtCo/C, tuned by electron transfer from Co to Pt and Pt lattice strain, was also found responsible for the weakened Pt-S interaction. The recovery test based on electro-oxidation suggested that PtCo/C also outperformed Pt/C with faster and more thorough release of HOR active sites. The SO42- species derived from electro-oxidation of S2- was more apt to adsorb on Pt/C than PtCo/C because of its stronger affinity to SO42- caused by the higher d-band center of Pt. Therefore, it is clarified that adequate modification of the Pt d-band center, for example, negatively tuned for the state-of-the-art Pt/C, is crucial to improve the sulfur resistance and recovery capability for Pt-based electrocatalysts while reserving comparable HOR activity. In particular, the investigated PtCo/C electrocatalyst is a better choice over Pt/C for more durable PEMFC anodes.

Surface Engineering of Carbon-Supported Platinum as a Route to Electrocatalysts with Superior Durability and Activity for PEMFC Cathodes.

Hydrogen fuel cells are regarded as a promising new carbon mitigation strategy to realize carbon neutrality. The exploitation of robust and efficient cathode catalysts is thus vital to the commercialization of proton exchange membrane fuel cells (PEMFCs). Herein, we demonstrate a facile and scalable surface engineering route to achieve superior durability and high activity of a Pt-based material as a PEMFC cathode catalyst through a controllable liquid-phase reduction approach. The proposed surface engineering strategy by modifying Pt/C reduces the oxygen content on the carbon support and also decreases the surface defects on Pt nanoparticles (NPs), which effectively alleviate the corrosion of carbon and inhibit the detachment, agglomeration, and growth of Pt NPs. The resulting catalyst exhibits superior durability after a 10,000 potential cycling test in an acid electrolyte─outperforming commercial Pt/C. Moreover, the catalyst also demonstrates an improved oxygen reduction reaction (ORR) activity in comparison to commercial Pt/C by virtue of the high content of metallic Pt and the weakened Pt-OH bonding that releases more Pt active sites for ORR catalysis. Most importantly, the developed catalyst shows outstanding PEMFC performance and excellent long-term durability over 50 h of a constant-current test and 100 h of a load-cycling operation. This effective route provides a new avenue for exploiting robust Pt-based catalysts with superior activity in practical applications of PEMFCs.

Conductive bimetal organic framework nanorods decorated with highly dispersed Co3O4nanoparticles as bi-functional electrocatalyst.

The poor electronic conductivity and low intrinsic electrocatalytic activity of metal organic frameworks (MOFs) greatly limit their direct application in electrocatalytic reactions. Herein, we report a conductive two-dimensionalπ-dconjugated Ni and Co bimetal organic framework (MOF)-NiCo-(2,3,6,7,10,11-hexaiminotriphenylene) (NiCo-HITP) nanorods decorated with highly dispersed Co3O4nanoparticles (NPs) as a promising bi-functional electrocatalyst towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) through an effective and facile strategy by modifying the rod-shaped -Ni3HITP2crystals using cobalt ions. The triggered electrocatalytic activity of the resulting MOF-based materials was achieved by increasing the electrical conductivity (7.23 S cm-1) originated from Ni3HITP2substrate and also by creating the cooperative catalysis sites of Co-Nxand Co3O4NPs. Optimized syntheses show a promising ORR activity with a high half-wave potential (0.77 V) and also a significantly improved OER activity compared with pure Ni3HITP2in alkaline electrolyte. Furthermore, a rechargeable Zn-air battery using the as-prepared material as air-cathode also shows a high power density (143.1 mW cm-2)-even comparable to a commercial Pt/C-RuO2-based battery. This methodology offers a new prospect in the design and synthesis of non-carbonized MOF bi-functional electrocatalysts for efficient catalysis towards ORR and OER.

Degradation Investigation of Electrocatalyst in Proton Exchange Membrane Fuel Cell at a High Energy Efficiency.

The development of high efficient stacks is critical for the wide spread application of proton exchange membrane fuel cells (PEMFCs) in transportation and stationary power plant. Currently, the favorable operation conditions of PEMFCs are with single cell voltage between 0.65 and 0.7 V, corresponding to energy efficiency lower than 57%. For the long term, PEMFCs need to be operated at higher voltage to increase the energy efficiency and thus promote the fuel economy for transportation and stationary applications. Herein, PEMFC single cell was investigated to demonstrate its capability to working with voltage and energy efficiency higher than 0.8 V and 65%, respectively. It was demonstrated that the PEMFC encountered a significant performance degradation after the 64 h operation. The cell voltage declined by more than 13% at the current density of 1000 mA cm-2, due to the electrode de-activation. The high operation potential of the cathode leads to the corrosion of carbon support and then causes the detachment of Pt nanoparticles, resulting in significant Pt agglomeration. The catalytic surface area of cathode Pt is thus reduced for oxygen reduction and the cell performance decreased. Therefore, electrochemically stable Pt catalyst is highly desirable for efficient PEMFCs operated under cell voltage higher than 0.8 V.

Gelatin-Derived 1D Carbon Nanofiber Architecture with Simultaneous Decoration of Single Fe-Nx Sites and Fe/Fe3 C Nanoparticles for Efficient Oxygen Reduction.

Exploring high-performance non-precious-metal electrocatalysts for the oxygen reduction reaction (ORR) is critical. Herein, a scalable and cost-effective strategy is reported for the construction of one-dimensional carbon nanofiber architectures with simultaneous decoration of single Fe-Nx sites and highly dispersed Fe/Fe3 C nanoparticles for efficient ORR, through the FeIII -complex-assisted electrospinning of gelatin nanofibers with subsequent pre-oxidation and carbonization. Results show that the presence of a FeIII complex enables the 1D gelatin nanofibers to be well retained during the pre-oxidation process. Owing to the distinct 1D nanofiber structure and the synergistic effect of Fe/Fe3 C and Fe-Nx sites, the resulting electrocatalyst is highly active for ORR with a half-wave potential of 0.885 V (outperforming commercial Pt/C) and a superior electrochemical stability in alkaline electrolytes. Similarly, it also shows a high power density (144.7 mW cm-2 ) and a superior stability in Zn-air batteries. This work opens a path for the design and synthesis of 1D carbon electrocatalyst for efficient ORR catalysis.

Phase Segregated Pt-SnO2 /C Nanohybrids for Highly Efficient Oxygen Reduction Electrocatalysis.

Strengthening the interfacial interaction in heterogeneous catalysts can lead to a dramatic improvement in their performance and allow the use of smaller amounts of active noble metal, thus decreasing the cost without compromising their activity. In this work, a facile phase-segregation method is demonstrated for synthesizing platinum-tin oxide hybrids supported on carbon black (PtSnO2 /C) in situ by air annealing PtSn alloy nanoparticles on carbon black. Compared with a control sample formed by preloading SnO2 on carbon support followed by deposition of Pt nanoparticles, the phase-segregation-derived PtSnO2 /C exhibits a more strongly coupled PtSnO2 interface with lattice overlap of Pt (111) and SnO2 (200), along with enhanced electron transfer from SnO2 to Pt. Furthermore, the PtSnO2 active sites show a strong ability to degrade reactive oxygen species. As a result, the PtSnO2 /C nanohybrids exhibit both excellent activity and stability as a catalyst for the oxygen reduction reaction, with an overall performance which is superior to both the control sample and commercial Pt/C catalyst. This phase-segregation method can be expected to be applicable in the preparation of other strongly coupled nanohybrids and offers a new route to high-performance heterogeneous catalysts for low-cost energy conversion devices.

Edge-Functionalized Polyphthalocyanine Networks with High Oxygen Reduction Reaction Activity.

Two-dimensional (2D) conjugated aromatic networks (CAN) have been fabricated by ball milling of polymeric cobalt phthalocyanine precursors edge-functionalized with different aromatic acid anhydride substituents. The optimal CAN, obtained by using tetraphenylphthalic anhydride, consists of uniform and thin (2.9 nm) layers with a high BET surface (92 m2 g-1), resulting in well-defined Co-N4 active sites with a high degree of exposure. Thence, this material exhibits excellent electrocatalytic oxygen reduction reaction (44 mA mgcat.-1). Compared to a benchmark Pt/C catalyst, this value denotes 1.2- and 6.0-fold enhancements, respectively, in terms of the mass of Pt and total Pt/C. When utilized as air electrode catalysts in Zn-air batteries, this material provides a maximum areal power density (137 mW cm-2) and mass power density (0.68 W mgcat.-1), values which also clearly surpass those of benchmark Pt/C catalyst. This support-free and pyrolysis-free strategy developed in this work delivers a novel route for the applications of 2D materials in clean energy conversion and storage.

Selective Loading of Atomic Platinum on a RuCeOx Support Enables Stable Hydrogen Evolution at High Current Densities.

High-performance electrocatalysts for the hydrogen evolution reaction (HER) have an important role to play in the development of renewable energy. Platinum remains the most efficient known HER electrocatalyst. Therefore, it is necessary to find ways to maximize Pt utilization in actual practical applications. Herein we demonstrate a facile strategy for synthesizing RuCeOx -supported, selectively loaded, atomic Pt (0.49 wt. %) (denoted Pt/RuCeOx -PA) by photoactivation at ambient temperature and pressure. Through the photoelectron transfer at the Mott-Schottky heterojunction in RuCeOx , Pt atoms became embedded into the RuO2 lattice. The resulting selectively loaded Pt-O-Ru moieties in Pt/RuCeOx -PA give a stronger hydrogen spillover effect than Pt complexes randomly loaded by either chemical activation or thermal activation. As a result, Pt/RuCeOx -PA shows superior HER performance to the materials prepared by random loading and is even better than a commercial Pt/C catalyst with much higher Pt loading (20 wt. %) at high current densities (from 50-600 mA cm-2 ).

Metal-Organic-Framework-Derived Co2 P Nanoparticle/Multi-Doped Porous Carbon as a Trifunctional Electrocatalyst.

Developing efficient and low-cost replacements for precious metals as electrocatalysts active in electrochemical reactions-the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR)-is a top priority in renewable energy technology. In this work a highly active and very stable trifunctional electrocatalyst composed of Co2 P embedded in Co, N, and P multi-doped carbon has been synthesized using zeolitic imidazolate frameworks as precursors. The synergistic effects between Co2 P and the multi-heteroatom-doped carbon substrates afford materials having electrocatalytic activities for HER, OER, and ORR, which are comparable-or even superior to-those of commercial RuO2 or Pt/C catalysts. Density functional theory calculations show that Co2 P has a higher density of states at the Fermi level than Con P (0 < n < 2), which promotes electron transfer and intermediates adsorption in the catalytic process. Zinc-air batteries and water splitting devices assembled using the materials as electrode electrocatalysts show good performance and outstanding stability. This work represents a breakthrough in improving the catalytic performance of non-precious metal electrocatalysts for OER, HER, and ORR, and opens new avenues for clean energy generation.

Prussian blue nanocubes decorated on nitrogen-doped hierarchically porous carbon network for efficient sorption of radioactive cesium.

Eliminating the radioactive 137Cs from nuclear waste is critical to the human health and environment. Prussian blue (PB)-based materials are considered as promising adsorbents for the removal of cesium. Herein, we demonstrate a facile strategy to achieve controllable synthesis of PB nanocrystals decorated on nitrogen-doped hierarchically porous carbon (NHPC) derived from cattle bone as adsorbent to remove cesium. The PB nanocrystals with a nanocube morphology are well distributed on NHPC, which is beneficial to increase the reachable surface area during adsorption. The resulting adsorbent exhibits a remarkable adsorption performance with a capacity of 125.31 mg g-1, a superior recyclability with 87 % of initial capacity retained after 5 cycles, and an outstanding adsorption selectivity for cesium. X-ray diffraction, X-ray photoelectron spectroscopy combined with 57Fe Mössbauer spectroscopy results reveal that cesium ions are inserted into the crystal channels of PB to generate a new phase (CsFe2(CN)6·3H2O) after adsorption. Moreover, the adsorption process is spontaneous and endothermic which can be described by the Langmuir isotherm and pseudo-second-order kinetic models. This strategy for synthesis of PB/carbon adsorbents offers efficient candidate for removal of 137Cs from wastewater.

Two-Dimensional Conjugated Aromatic Networks as High-Site-Density and Single-Atom Electrocatalysts for the Oxygen Reduction Reaction.

Two-dimensional conjugated aromatic networks (CAN) with ultra-thin conjugated layers (ca. 3.5 nm) and high single-metal-atom-site density (mass content of 10.7 wt %, and 0.73 metal atoms per nm2 ) are prepared via a facile pyrolysis-free route involving a one-step ball milling of the solid-phase-synthesized polyphthalocyanine. These materials display outstanding oxygen reduction reaction (ORR) mass activity of 47 mA mgcat. -1 represents 1.3- and 6.4-fold enhancements compared to Pt and Pt/C in benchmark Pt/C, respectively. Moreover, the primary Zn-air batteries constructed with CAN as an air electrode demonstrate a mass/volume power density of 880 W gcat. -1 /615 W cmcat. -3 and stable long-term operation for 100 h. This strategy offers a new way to design high-performance electrocatalysts with atomic precision for use in other energy-storage and conversion applications.

Ice/Salt-Assisted Synthesis of Ultrathin Two-Dimensional Micro/Mesoporous Iron and Nitrogen Co-Doped Carbon as an Efficient Electrocatalyst for Oxygen Reduction.

An ice/salt-assisted strategy has been developed to achieve the green and efficient synthesis of ultrathin two-dimensional (2D) micro/mesoporous carbon nanosheets (CNS) with the dominant active moieties of Fe-N4 (Fe-N-CNS) as high-performance electrocatalysts for the oxygen reduction reaction (ORR). The strategy involves freeze-drying a mixture of iron porphyrin and KCl salt using ice as template followed by a confined pyrolysis with KCl as an independent sealed nanoreactor to facilitate the formation of 2D carbon nanosheets, N incorporation, and porosity creation. The well-defined assembly of ultrathin 2D carbon nanosheets ensures high utilization of D1 and D3 Fe-N4 active sites, and effectively promotes the mass transport of ORR reactants by virtue of the pronounced mesoporous structure. The resulting Fe-N-CNS electrocatalyst was shown to exhibit superior ORR activity, better electrochemical durability, and methanol tolerance towards ORR in alkaline electrolyte relative to the commercial Pt/C electrocatalyst.

Sustainable Carbonaceous Materials Derived from Biomass as Metal-Free Electrocatalysts.

Although carbon is the second most abundant element in the biosphere, a large proportion of the available carbon resources in biomass from agriculture, stock farming, ocean fisheries, and other human activities is currently wasted. The use of sustainable carbonaceous materials as an alternative to precious metals in electrocatalysis is a promising pathway for transforming sustainable biomass resources into sustainable energy-conversion systems. The development of rational syntheses of metal-free carbonaceous catalysts derived from sustainable biomass has therefore become a topic of significant interest in materials chemistry. However, great efforts are still required to develop methods that are low cost, scalable, and environmentally friendly and which afford carbonaceous materials having an electrocatalytic performance comparable to, or even better than, existing precious metal catalysts. Herein, recent achievements in developing metal-free carbonaceous catalysts based on biomass are reviewed and discussed and the critical issues which still need to be addressed are highlighted. The focus is on representative synthesis and optimization strategies applicable to different kinds of biomass, as well as studies of the physicochemical structure and electrochemical performance of the resulting metal-free carbonaceous catalysts. Finally, some guidelines for the future development of this important area are provided.

Template-Free Synthesis of Two-Dimensional Fe/N Codoped Carbon Networks as Efficient Oxygen Reduction Reaction Electrocatalysts.

A direct pyrolysis and template-free synthesis strategy is demonstrated to synthesize the two-dimensional (2-D) Fe/N codoped carbon networks by virtue of 2-D graphitic-carbon nitride (g-C3N4) intermediates derived from melamine. Because of the stabilization and steric hindrance of additional N ligands with bisnitrogen-containing groups (phenanthroline, phthalonitrile, and phenylenediamine), the thin graphitic-layered Fe/N codoped carbon materials have successfully inherited the 2-D morphology from the g-C3N4 intermediate after direct carbonization treatment. After the easy removal of inactive Fe particles, the resultant sample exhibits numerous well-dispersed Fe atoms embedded in the carbon layers with a hierarchical (meso- and micro-) porous structure. Owing to the high active site density and open porous structure, the thin graphitic-layered Fe/N codoped carbon electrocatalysts exhibit superior oxygen reduction reaction performance (a half-wave potential of 0.88 V and a kinetics current density of 3.8 mA cm-2), even better than the commercial Pt/C catalysts (0.85 V and 1.6 mA cm-2, respectively). The facile and effective synthesis strategy without template to build the graphene-like nanoarchitectures inherited from the 2-D intermediates will lead to a great development of 2-D carbon materials in various electrochemical applications.

Bimetal Zeolitic Imidazolite Framework-Derived Iron-, Cobalt- and Nitrogen-Codoped Carbon Nanopolyhedra Electrocatalyst for Efficient Oxygen Reduction.

Replacing precious metal electrocatalysts with high-performance and low-cost nonprecious metal electrocatalysts (NPMCs) is crucial for the commercialization of fuel cell technologies. Herein, we present a novel and facile route for synthesis of iron-, cobalt-, and nitrogen-codoped carbon nanopolyhedra electrocatalysts (Fe,Co,N-CNP) by one-step pyrolysis of a new type of Fe/Co bimetal zeolitic imidazolate framework (Fe,Co-ZIF) crystals that were self-assembled by oxygen-free solvothermal reaction of Fe2+ and Co2+ with 2-methylimidazole. During the pyrolysis process, the Fe2+ ions in Fe,Co-ZIF not only effectively inhibit the aggregation of Co nanoparticles but also increase the specific surface area (SSA) and N content of the resultant electrocatalysts. The optimized Fe,Co,N-CNP(0.3) (Fe/Co molar ratio of 0.3 in Fe,Co-ZIF) electrocatalyst exhibited a highly promising activity for oxygen reduction reaction (ORR) with a positive half-wave potential ( E1/2) of 0.875 V (29 mV higher than that of the commercial Pt/C), excellent methanol tolerance, and electrochemical stability in the alkaline electrolyte. Also, Fe,Co,N-CNP(0.3) presents comparable ORR catalytic activity as Pt/C in the acidic electrolyte with E1/2 of 0.764 V and superior methanol tolerance and electrochemical stability. The outstanding ORR performance of Fe,Co,N-CNP(0.3) is ascribed to the synergistic contribution of homogeneous Fe, Co, and N codoping structure, high SSA, and hierarchically porous structure for rapid mass transport. This novel and rational methodology for controlled synthesis of ZIFs-derived nitrogen-doped porous carbon nanopolyhedras offers new prospects in developing highly efficient NPMCs for ORR.