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1.
The future large‐scale deployment of rechargeable zinc–air batteries requires the development of cheap, stable, and efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In this work, a highly efficient bifunctional electrocatalyst is prepared by depositing 3–5 nm NiFe layered double hydroxide (NiFe‐LDH) nanoparticles on Co,N‐codoped carbon nanoframes (Co,N‐CNF). The NiFe‐LDH/Co,N‐CNF electrocatalyst displayed an OER overpotential of 0.312 V at 10 mA cm?2 and an ORR half‐wave potential of 0.790 V. The outstanding performance of the electrocatalyst is attributable to the high electrical conductivity and excellent ORR activity of Co,N‐CNF, together with the strong anchoring of 3–5 nm NiFe‐LDH nanoparticles, which preserves active sites. Inspired by the excellent OER and ORR performance of NiFe‐LDH/Co,N‐CNF, a prototype rechargeable zinc–air battery is developed. The battery exhibited a low discharge–charge voltage gap (1.0 V at 25 mA cm?2) and long‐term cycling durability (over 80 h), and superior overall performance to a counterpart battery constructed using a mixture of IrO2 and Pt/C as the cathode. The strategy developed here can easily be adapted to synthesize other bifunctional CNF‐based hybrid electrodes for ORR and OER, providing a practical route to more efficient rechargeable zinc–air batteries.  相似文献   

2.
Currently, it is still a significant challenge to simultaneously boost various reactions by one electrocatalyst with high activity, excellent durability, as well as low cost. Herein, hybrid trifunctional electrocatalysts are explored via a facile one‐pot strategy toward an efficient oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The catalysts are rationally designed to be composed by FeCo nanoparticles encapsuled in graphitic carbon films, Co2P nanoparticles, and N,P‐codoped carbon nanofiber networks. The FeCo nanoparticles and the synergistic effect from Co2P and FeCo nanoparticles make the dominant contributions to the ORR, OER, and HER activities, respectively. Their bifunctional activity parameter (?E) for ORR and OER is low to 0.77 V, which is much smaller than those of most nonprecious metal catalysts ever reported, and comparable with state‐of‐the‐art Pt/C and RuO2 (0.78 V). Accordingly, the as‐assembled Zn–air battery exhibits a high power density of 154 mW cm?2 with a low charge–discharge voltage gap of 0.83 V (at 10 mA cm?2) and excellent stability. The as‐constructed overall water‐splitting cell achieves a current density of 10 mA cm?2 (at 1.68 V), which is comparable to the best reported trifunctional catalysts.  相似文献   

3.
Bifunctional oxygen catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with high activities and low‐cost are of prime importance and challenging in the development of fuel cells and rechargeable metal–air batteries. This study reports a porous carbon nanomaterial loaded with cobalt nanoparticles (Co@NC‐x/y) derived from pyrolysis of a Co/Zn bimetallic zeolitic imidazolite framework, which exhibits incredibly high activity as bifunctional oxygen catalysts. For instance, the optimal catalyst of Co@NC‐3/1 has the interconnected framework structure between porous carbon and embedded carbon nanotubes, which shows the superb ORR activity with onset potential of ≈1.15 V and half‐wave potential of ≈0.93 V. Moreover, it presents high OER activity that can be further enhanced to over commercial RuO2 by P‐doped with overpotentials of 1.57 V versus reversible hydrogen electrode at 10 mA cm?2 and long‐term stability for 2000 circles and a Tafel slope of 85 mV dec?1. Significantly, the nanomaterial demonstrates better catalytic performance and durability than Pt/C for ORR and commercial RuO2 and IrO2 for OER. These findings suggest the importance of a synergistic effect of graphitic carbon, nanotubes, exposed Co–Nx active sites, and interconnected framework structure of various carbons for bifunctional oxygen electrocatalysts.  相似文献   

4.
Developing earth‐abundant and active electrocatalysts for the oxygen evolution reaction (OER) as replacements for conventional noble metal catalysts is of scientific and technological importance for achieving cost‐effective and efficient conversion and storage of renewable energy. However, most of the promising candidates thus far are exclusively metal‐based catalysts, which are disadvantaged by relatively restricted electron mobility, corrosion susceptibility, and detrimental environmental influences. Herein, hierarchically porous nitrogen (N) and phosphorus (P) codoped carbon nanofibers directly grown on conductive carbon paper are prepared through an electrochemically induced polymerization process in the presence of aniline monomer and phosphonic acid. The resultant material exhibits robust stability (little activity attenuation after 12 h continuous operation) and high activity with low overpotential (310 mV at 10 mA cm?2) toward electrocatalytic oxygen production, with performance comparable to that of the precious iridium oxide (IrO2) benchmark. Experimental measurements reveal that dual doping of N and P can result in an increased active surface area and abundant active sites in comparison with the single doped and pristine carbon counterparts, and density functional theory calculations indicate that N and P dopants can coactivate the adjacent C atoms, inducing synergistically enhanced activity toward OER.  相似文献   

5.
Transition metal atoms with corresponding nitrogen coordination are widely proposed as catalytic centers for the oxygen reduction reaction (ORR) in metal–nitrogen–carbon (M–N–C) catalysts. Here, an effective strategy that can tailor Fe–N–C catalysts to simultaneously enrich the number of active sites while boosting their intrinsic activity and utilization is reported. This is achieved by edge engineering of FeN4 sites via a simple ammonium chloride salt‐assisted approach, where a high fraction of FeN4 sites are preferentially generated and hosted in a graphene‐like porous scaffold. Theoretical calculations reveal that the FeN4 moieties with adjacent pore defects are likely to be more active than the nondefective configuration. Coupled with the facilitated accessibility of active sites, this prepared catalyst, when applied in a practical H2–air proton exchange membrane fuel cell, delivers a remarkable peak power density of 0.43 W cm?2, ranking it as one of the most active M–N–C catalysts reported to date. This work provides a new avenue for boosting ORR activity by edge manipulation of FeN4 sites.  相似文献   

6.
Development of highly active and stable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts from earth‐abundant elements remains a grand challenge for highly demanded reversible fuel cells and metal–air batteries. Carbon catalysts have many advantages over others due to their low cost, excellent electrical conductivity, high surface area, and easy functionalization. However, they typically cannot withstand the highly oxidative OER environment. Here, a new class of bifunctional electrocatalyst is reported, consisting of ultralarge sized nitrogen doped graphene tubes (N‐GTs) (>500 nm) decorated with FeCoNi alloy particles. These tubes are prepared from an inexpensive precursor, dicyandiamide, via a template‐free graphitization process. The ORR/OER activity and the stability of these graphene tube catalysts depend strongly on the transition metal precursors. The best performing FeCoNi‐derived N‐GT catalyst exhibits excellent ORR and OER activity along with adequate electrochemical durability over a wide potential window (0–1.9 V) in alkaline media. The measured OER current is solely due to desirable O2 evolution, rather than carbon oxidation. Extensive electrochemical and physical characterization indicated that high graphitization degree, thicker tube walls, proper nitrogen doping, and presence of FeCoNi alloy particles are vital for high bifunctional activity and electrochemical durability of tubular carbon catalysts.  相似文献   

7.
Development of inexpensive and efficient oxygen evolution reaction (OER) catalysts in acidic environment is very challenging, but it is important for practical proton exchange membrane water electrolyzers. A molecular iron–nitrogen coordinated carbon nanofiber is developed, which is supported on an electrochemically exfoliated graphene (FeN4/NF/EG) electrocatalyst through carbonizing the precursor composed of iron ions absorbed on polyaniline‐electrodeposited EG. Benefitting from the unique 3D structure, the FeN4/NF/EG hybrid exhibits a low overpotential of ≈294 mV at 10 mA cm?2 for the OER in acidic electrolyte, which is much lower than that of commercial Ir/C catalysts (320 mV) as well as all previously reported acid transitional metal‐derived OER electrocatalysts. X‐ray absorption spectroscopy coupled with a designed poisoning experiment reveals that the molecular Fe? N4 species are identified as active centers for the OER in acid. The first‐principles‐based calculations verify that the Fe? N4–doped carbon structure is capable of reducing the potential barriers and boosting the electrocatalytic OER activity in acid.  相似文献   

8.
Development of inexpensive and efficient oxygen evolution reaction (OER) catalysts in acidic environment is very challenging, but it is important for practical proton exchange membrane water electrolyzers. A molecular iron–nitrogen coordinated carbon nanofiber is developed, which is supported on an electrochemically exfoliated graphene (FeN4/NF/EG) electrocatalyst through carbonizing the precursor composed of iron ions absorbed on polyaniline‐electrodeposited EG. Benefitting from the unique 3D structure, the FeN4/NF/EG hybrid exhibits a low overpotential of ≈294 mV at 10 mA cm?2 for the OER in acidic electrolyte, which is much lower than that of commercial Ir/C catalysts (320 mV) as well as all previously reported acid transitional metal‐derived OER electrocatalysts. X‐ray absorption spectroscopy coupled with a designed poisoning experiment reveals that the molecular Fe?N4 species are identified as active centers for the OER in acid. The first‐principles‐based calculations verify that the Fe?N4–doped carbon structure is capable of reducing the potential barriers and boosting the electrocatalytic OER activity in acid.  相似文献   

9.
To arrive to sustainable hydrogen‐based energy solutions, the understanding of water‐splitting catalysts plays the most crucial role. Herein, state‐of‐the‐art hypotheses are combined on electrocatalytic active metal sites toward the oxygen evolution reaction (OER) to develop a highly efficient catalyst based on Earth‐abundant cobalt and zinc oxides. The precursor catalyst Zn0.35Co0.65O is synthesized via a fast microwave‐assisted approach at low temperatures. Subsequently, it transforms in situ from the wurtzite structure to the layered γ‐Co(O)OH, while most of its zinc leaches out. This material shows outstanding catalytic performance and stability toward the OER in 1 m KOH (overpotential at 10 mA cm?2 ηinitial = 306 mV, η98 h = 318 mV). By comparing the electrochemical results and ex situ analyses to today's literature, clear structure‐activity correlations are able to be identified. The findings suggest that coordinately unsaturated cobalt octahedra on the surface are indeed the active centers for the OER.  相似文献   

10.
Construction of well‐defined metal–organic framework precursor is vital to derive highly efficient transition metal–carbon‐based electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Herein, a novel strategy involving an in situ transformation of ultrathin cobalt layered double hydroxide into 2D cobalt zeolitic imidazolate framework (ZIF‐67) nanosheets grafted with 3D ZIF‐67 polyhedra supported on the surface of carbon cloth (2D/3D ZIF‐67@CC) precursor is proposed. After a low‐temperature pyrolysis, this precursor can be further converted into hybrid composites composed of ultrafine cobalt nanoparticles embedded within 2D N‐doped carbon nanosheets and 3D N‐doped hollow carbon polyhedra (Co@N‐CS/N‐HCP@CC). Experimental and density functional theory calculations results indicate that such composites have the advantages of a large number of accessible active sites, accelerated charge/mass transfer ability, the synergistic effect of components as well as an optimal water adsorption energy change. As a result, the obtained Co@N‐CS/N‐HCP@CC catalyst requires overpotentials of only 66 and 248 mV to reach a current density of 10 mA cm?2 for HER and OER in 1.0 m KOH, respectively. Remarkably, it enables an alkali‐electrolyzer with a current density of 10 mA cm?2 at a low cell voltage of 1.545 V, superior to that of the IrO2@CC||Pt/C@CC couple (1.592 V).  相似文献   

11.
The development of efficient and robust earth‐abundant electrocatalysts for the oxygen evolution reaction (OER) is an ongoing challenge. Here, a novel and stable trimetallic NiFeCr layered double hydroxide (LDH) electrocatalyst for improving OER kinetics is rationally designed and synthesized. Electrochemical testing of a series of trimetallic NiFeCr LDH materials at similar catalyst loading and electrochemical surface area shows that the molar ratio Ni:Fe:Cr = 6:2:1 exhibits the best intrinsic OER catalytic activity compared to other NiFeCr LDH compositions. Furthermore, these nanostructures are directly grown on conductive carbon paper for a high surface area 3D electrode that can achieve a catalytic current density of 25 mA cm?2 at an overpotential as low as 225 mV and a small Tafel slope of 69 mV dec?1 in alkaline electrolyte. The optimized NiFeCr catalyst is stable under OER conditions and X‐ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, and elemental analysis confirm the stability of trimetallic NiFeCr LDH after electrochemical testing. Due to the synergistic interactions among the metal centers, trimetallic NiFeCr LDH is significantly more active than NiFe LDH and among the most active OER catalysts to date. This work also presents general strategies to design more efficient metal oxide/hydroxide OER electrocatalysts.  相似文献   

12.
Effectively active oxygen evolution reaction (OER) electrocatalysts are highly desired for water splitting. Herein, the design and fabrication of nanometer‐sized Fe‐modulated CoOOH nanoparticles by a novel conversion tailoring strategy is reported for the first time and these nanoparticles are assembled on graphene matrix to construct 2D nanohybrids (Fe? CoOOH/G) with ultrasmall particles and finely modulated local electronic structure of Co cations. The Fe components are capable of tailoring and converting the micrometer‐sized sheets into nanometer‐sized particles, indicative of ultrasensitive Fe‐triggered behavior. The as‐made Fe? CoOOH/G features highly exposed edge active sites, well‐defined porous structure, and finely modulated electron structure, together with effectively interconnected conducting networks endowed by graphene. Density functional theory calculations have revealed that the Fe dopants in the Fe? CoOOH nanoparticles have an enhanced adsorption capability toward the oxygenated intermediates involved in OER process, thus facilitating the whole catalytic reactions. Benefiting from these integrated characteristics, the as‐made Fe? CoOOH/G nanohybrids as an oxygen evolution electrocatalyst can deliver a low overpotential of 330 mV at 10 mA cm?2 and excellent electrochemical durability in alkaline medium. This strategy provides an effective, durable, and nonprecious‐metal electrocatalyst for water splitting.  相似文献   

13.
The oxidation of water to produce oxygen gas is related to a variety of energy storage systems. Thus, the development of efficient, cheap, durable, and scalable electrocatalysts for oxygen evolution reaction (OER) is of great importance. Here, a high‐performance OER catalyst, nitrogen and sulfur codoped graphite foam (NSGF) is reported. This NSGF is prepared from commercial graphite foil and directly applied as an electrocatalytic electrode without using a current collector and a polymeric binder. It exhibits an extremely low overpotential of 0.380 V to reach a current density of 10 mA cm?2 and shows fast kinetics with a small Tafel slope of 96 mV dec?1 in 0.1 m KOH. This electrocatalytic performance is superior or comparable to those of previously reported metal‐free OER catalysts.  相似文献   

14.
Electrochemical splitting of water is an attractive way to produce hydrogen fuel as a clean and renewable energy source. However, a major challenge is to accelerate the sluggish kinetics of the anodic half‐cell reaction where oxygen evolution reaction (OER) takes place. Here, a seamlessly conductive 3D architecture is reported with a carbon‐shelled Ni‐Co nanowire network as a highly efficient OER electrocatalyst. Highly porous and granular Ni‐Co nanowires are first grown on a carbon fiber woven fabric utilizing a cost‐effective hydrothermal method and then conductive carbon shell is coated on the Ni‐Co nanowires via glucose carbonization and annealing processes. The conductive carbon layer surrounding the nanowires is introduced to provide a continuous pathway for facile electron transport throughout the whole of the integrated 3D catalyst. This 3D hierarchical structure provides several synergistic effects and beneficial functions including a large number of active sites, easy accessibility of water, fast electron transport, rapid release of oxygen gas, enhanced electrochemical durability, and stronger structural integrity, resulting in a remarkable OER activity that delivers an overpotential of 302 mV with a Tafel slope of 43.6 mV dec?1 at a current density of 10 mA cm?2 in an alkaline medium electrolyte (1 m KOH).  相似文献   

15.
The development of dual catalysts with high efficiency toward oxygen reduction and evolution reactions (ORR and OER) in acidic media is a significant challenge. Here an active and durable dual catalyst based upon cubic Pt39Ir10Pd11 nanocages with an average edge length of 12.3 nm, porous walls as thin as 1.0 nm, and well‐defined {100} facets is reported. The trimetallic nanocages perform better than all the reported dual catalysts in acidic media, with a low ORR‐OER overpotential gap of only 704 mV at a Pt‐Ir‐Pd loading of 16.8 µgPt+Ir+Pd cm?2geo. For ORR at 0.9 V, when benchmarked against the commercial Pt/C and Pt‐Pd nanocages, the trimetallic nanocages exhibit an enhanced mass activity of 0.52 A mg?1Pt+Ir+Pd (about four and two times as high as those of the Pt/C and Pt‐Pd nanocages) and much improved durability. For OER, the trimetallic nanocages show a remarkable mass activity of 0.20 A mg?1Pt+Ir at 1.53 V, which is 16.7 and 4.3 fold relative to those of the Pt/C and Pt‐Pd nanocages, respectively. These improvements can be ascribed to the highly open structure of the nanocages, and the possible electronic coupling between Ir and Pt atoms in the lattice.  相似文献   

16.
It is of great significance to develop highly efficient and superior stable oxygen evolution reaction (OER) electrocatalysts for upcoming electrochemical conversion technologies and clean energy systems. Here, an assembled 3D electrode is synthesized by a one‐step solvothermal process using such an original OER electrocatalyst. During the solvothermal process, Ni ions released from Ni foam in acidic solution and Fe ions added exogenously act as metal centers and coordinate with terephthalic acid (TPA) organic molecules by robust coordinate bonds, and finally, NiFe‐based metal–organic framework (MOF) nanosheets in situ grown on Ni foam, i.e., MIL‐53(FeNi)/NF, are prepared. This binder‐free 3D electrode shows superior OER activity with high current density (50 mA cm?2) at an overpotential of 233 mV, a Tafel slope of 31.3 mV dec?1, and excellent stability in alkaline aqueous solution (1 m KOH). It is discovered that introduction of Fe into MIL‐53 structure increases electrochemically‐active areas as well as reaction sites, accelerated electron transport capability, and modulated electronic structure to enhance catalytic performance. Besides, first principles calculations show that MIL‐53(FeNi) is more favorable for foreign atoms' adsorption and has increased 3d orbital electron density boosting intrinsic activity. This work elucidates a promising electrode for electrocatalysts and enriches direct application of MOF materials.  相似文献   

17.
The low hydrogen adsorption free energy and strong acid/alkaline resistance of layered MoS2 render it an excellent pH‐universal electrocatalyst for hydrogen evolution reaction (HER). However, the catalytic activity is dominantly suppressed by its limited active‐edge‐site density. Herein, a new strategy is reported for making a class of strongly coupled MoS2 nanosheet–carbon macroporous hybrid catalysts with engineered unsaturated sulfur edges for boosting HER catalysis by controlling the precursor decomposition and subsequent sodiation/desodiation. Both surface chemical state analysis and first‐principles calculations verify that the resultant catalysts exhibit a desirable valence‐electron state with high exposure of unsaturated sulfur edges and an optimized hydrogen adsorption free energy, significantly improving the intrinsic HER catalytic activity. Such an electrocatalyst exhibits superior and stable catalytic activity toward HER with small overpotentials of 136 mV in 0.5 m H2SO4 and 155 mV in 1 m KOH at 10 mA cm?2, which is the best report for MoS2–C hybrid electrocatalysts to date. This work paves a new avenue to improve the intrinsic catalytic activity of 2D materials for hydrogen generation.  相似文献   

18.
Rational design and massive production of bifunctional catalysts with superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are essential for developing metal–air batteries and fuel cells. Herein, controllable large‐scale synthesis of sulfur‐doped CaMnO3 nanotubes is demonstrated via an electrospinning technique followed by calcination and sulfurization treatment. The sulfur doping can not only replace oxygen atoms to increase intrinsic electrical conductivity but also introduce abundant oxygen vacancies to provide enough catalytically active sites, which is further demonstrated by density functional theory calculation. The resulting sulfur‐modified CaMnO3 (CMO/S) exhibits better electrocatalytic activity for ORR and OER in alkaline solution with higher stability performance than the pristine CMO. These results highlight the importance of sulfur treatment as a facile yet effective strategy to improve the ORR and OER catalytic activity of the pristine CaMnO3. As a proof‐of‐concept, a rechargeable Zn–air battery using the bifunctional catalyst exhibits a small charge–discharge voltage polarization, and long cycling life. Furthermore, a solid‐state flexible and rechargeable Zn–air battery gives superior discharge–charge performance and remarkable stability. Therefore, the CMO/S nanotubes might be a promising replacement to the Pt‐based electrocatalysts for metal–air batteries and fuel cells.  相似文献   

19.
The development of efficient and abundant water oxidation catalysts is essential for the large‐scale storage of renewable energy in the form of hydrogen fuel via electrolytic water splitting, but still remains challenging. Based upon eutectic reaction and dealloying inheritance effect, herein, novel Ni‐Fe‐O‐based composite with a unique mesoporous nanowire network structure is designed and synthesized. The composite exhibits exceptionally low overpotential (10 mA cm?2 at an overpotential of 244 mV), low Tafel slope (39 mV dec?1), and superior long‐term stability (remains 10 mA cm?2 for over 60 h without degradation) toward oxygen evolution reaction (OER) in 1 m KOH. Moreover, an alkaline water electrolyzer is constructed with the Ni‐Fe‐O composite as catalyst for both anode and cathode. This electrolyzer displays superior electrolysis performance (affording 10 mA cm?2 at 1.64 V) and long‐term durability. The remarkable features of the catalyst lie in its unique mesoporous nanowire network architecture and the synergistic effect of the metal core and the active metal oxide, giving rise to the strikingly enhanced active surface area, accelerated electron/ion transport, and further promoted reaction kinetics of OER.  相似文献   

20.
As a cost‐effective catalyst for the oxygen evolution reaction (OER), the potential use of FeOOH is hindered by its intrinsic poor electron conductivity. Here, the significant enhancement of OER activity and long‐term stability of electrodeposited FeOOH on zeolitic imidazolate framework‐derived N‐doped porous carbons (NPCs) are reported. In alkaline media, FeOOH/NPC supported on nickel foam as a 3D electrode delivers a current density of 100 mA cm?2 at a small overpotential of 230 mV and exhibits a low Tafel slope of 33.8 mV dec?1 as well as excellent durability, making it one of the most active OER catalysts. Such high performance is attributed to a combined effect of the excellent electron conductivity of NPC and the synergy between FeOOH and NiO derived from Ni substrate.  相似文献   

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