RESUMEN
Spin engineering is a promising way to modulate the interaction between the metal d-orbital and the intermediates and thus enhance the catalytic kinetics. Herein, an innovative strategy is reported to modulate the spin state of Co by regulating its coordinating environment. o-c-CoSe2 -Ni is prepared as pre-catalyst, then in situ electrochemical impedance spectroscopy (EIS) and in situ Raman spectroscopy are employed to prove phase transition, and CoOOH/Co3 O4 is formed on the surface as active sites. In hybrid water electrolysis, the voltage has a negative shift, and in zinc-ethanol-air battery, the charging voltage is lowered and the cycling stability is greatly increased. Coordinated atom substitution and crystalline symmetry change are combined to regulate the absorption ability of reaction intermediates with balanced optimal adsorption. Coordinated atom substitution weakens the adsorption while the crystalline symmetry change strengthens the adsorption. Importantly, the tetrahedral sites are introduced by Ni doping which enables the co-existence of four-coordinated sites and six-coordination sites in o-c-CoSe2 -Ni. The dz2 + dx2 -y2 orbital occupancy decreases after the atomic substitution, while increases after replacing the CoSe6 -Oh field with CoSe6 -Oh /CoSe4 -Td . This work explores a new direction for the preparation of efficient catalysts for water electrolysis and innovative zinc-ethanol-air battery.
RESUMEN
Designing bifunctional low-cost photo-assisted electrocatalysts for converting solar and electric energy into hydrogen energy remains a huge challenge. Herein, a heterojunction (Fe cluster modified Co9 S8 loaded on carbon nanotubes, Co9 S8 -Fe@CNT) for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is demonstrated. Benefiting from the good electronic conductivity and spatial confinement of the carbon skeleton, as well as the electronic structure regulation of the Fe cluster, Co9 S8 -Fe@CNT exhibits excellent catalytic performance with a low overpotential of 150 mV for OER and 135 mV for HER at 10 mA cm-2 . Upon light irradiation, holes and electrons are generated in the valence band and conduction band of the Co9 S8 , respectively. Part of the charges are transferred to the interface to facilitate the catalytic reaction, while the remaining are transferred by the electrode. When working as a bifunctional catalyst for overall water splitting, the performance can reach 1.33 V at under light conditions, which is significantly better than 1.52 V in a dark environment. Theoretical calculations revealed lowered Gibbs free energy (∆GH *) of the heterojunction with the effect of Fe modification of Co9 S8 . This work sheds a new light in designing novel photoelectrochemical materials to convert solar and electric energy into chemical energy.
RESUMEN
To overcome the low efficiency of overall water splitting, highly effective and stable catalysts are in urgent need, especially for the anode oxygen evolution reaction (OER). In this case, nickel selenides appear as good candidates to catalyze OER and other substitutable anodic reactions due to their high electronic conductivity and easily tunable electronic structure to meet the optimized adsorption ability. Herein, an interesting phase transition from the hexagonal phase of NiSe (H-NiSe) to the rhombohedral phase of NiSe (R-NiSe) induced by the doping of cobalt atoms is reported. The five-coordinated R-NiSe is found to grow adjacent to the six-coordinated H-NiSe, resulting in the formation of the H-NiSe/R-NiSe heterostructure. Further characterizations and calculations prove the reduced splitting energy for R-NiSe and thus the less occupancy in the t2g orbits, which can facilitate the electron transfer process. As a result, the Co2 -NiSe/NF shows a satisfying catalytic performance toward OER, hydrogen evolution reaction, and (hybrid) overall water splitting. This work proves that trace amounts of Co doping can induce the phase transition from H-NiSe to R-NiSe. The formation of less-coordinated species can reduce the t2g occupancy and thus enhance the catalytic performance, which might guide rational material design.
RESUMEN
The development of bifunctional catalysts that facilitate both the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) in alkaline environment is crucial for realizing unitized regenerative anion-exchange membrane fuel cells. In this study, a novel strategy to modulate the electron density of MoO3 through Ni doping (sample named Nix Mo1- x O3 ) is reported. Ni is incorporated to replace Mo atoms in MoO3 . Specifically, Nix Mo1- x O3 is combined with optimal adsorption energy, along with MoO2 /Mo2 N hybrid with high conductivity. The resulting Nix Mo1- x O3 supported on MoO2 /Mo2 N hybrid (sample named as Nix Mo1- x O3 -H) exhibits excellent alkaline HER activity, with an overpotential of only 16 mV at 10 mA cm-2 and a Tafel slope of 54 mV dec-1 . In addition, the Nix Mo1- x O3 -H demonstrates an ultrahigh HOR performance with a high exchange current density (3.852 mA cm-2 ). The catalyst's breakdown potential of 0.23 V indicates its ability to withstand higher voltages without breaking down. As evidenced by the results, this characteristic leads to improved stability. These results are higher than those of the other catalysts reported, which indicates that the electron density of MoO3 can be effectively modulated through Ni doping, leading to excellent HER and HOR performance.
RESUMEN
By doping Ni into m-CoSeO3, the structure of the catalyst was modified to improve the Ethanol Oxidation Reaction (EOR) catalytic performance. The catalyst exhibited excellent EOR catalytic activity (j10 = 1.35 V) and high stability. Therefore, this catalyst is used in an innovative zinc-ethanol-air battery, which is more efficient and stable than the traditional zinc-air battery.
RESUMEN
It is a good idea for efficient production of hydrogen to use ethanol oxidation reaction (EOR) in place of oxygen evolution reaction (OER) in water electrolysis process. Ni-based non-precious electrocatalysts are widely used in the conversion of ethanol to acetic acid. Here, different selenide heterostructures (NiCoSe, NiFeSe, and NiCuSe) are prepared in which Ni sites are regulated by transition metal. The valence state of Ni is NiCuSe < NiCoSe < NiFeSe in the three heterojunctions. NiCoSe shows the optimized charge distribution of Ni sites and outstanding catalytic activity. The effective modulations lead to optimized d-band center and facilitates both adsorption and desorption of reaction intermediates, which improves the kinetics of EOR. The results of this work prove that with appropriate designed catalyst it is possible to replace kinetically slow OER with faster EOR in water electrolysis to produce hydrogen.
RESUMEN
The development of hydrogen energy is limited by the high cost of platinum group metals (PGM). There is an urgent need to design efficient PGM-free electrocatalysts in the hydrogen electrode. Herein, Janus Ni/W bimetallic materials are proposed as an effective PGM-free bifunctional hydrogen electrocatalyst. By constructing the bimetallic materials, a synergistic effect is realized to enhance the reaction kinetics and improve the catalytic performance. In general, Ni can provide excellent Had sites, and W serves as OHad sites. Therefore, the synergistic effect of Ni and W can improve the kinetics of hydrogen evolution reaction and the hydroxide oxidation reaction. Ni/W@NF can obtain the hydrogen evolution reaction current density of 10 mA cm-2 with an overpotential of only 62.6 mV, and the exchange current density of hydroxide oxidation reaction can reach 1.83 mA cm-2. This work provides a new idea for the design of high-efficiency and low-cost PGM-free bifunctional hydrogen electrocatalysts.
RESUMEN
The earth-abundant iron and nitrogen doped carbon (Fe-N-C) catalyst has great potential to substitute noble metal catalysts for oxygen reduction reaction (ORR) in H2-O2 proton exchange membrane fuel cells (PEMFCs). Herein, we report the preparation of Fe-N4 moiety doped carbon nanotubes (CNTs) by ball milling and two-step pyrolysis with dual metal-organic frameworks (MOFs) as the precursor. This catalyst shows high ORR catalytic performance and stability. Different from traditional inorganic iron sources, the MOF structure can effectively prevent the iron metal from aggregating during pyrolysis. In PEMFC, the catalyst shows high current density (0.39 A/cm2 at 0.7 V) and power density (850 mW/cm2). Such a method brings inspiration for the reasonable design of FeNC catalysts with high catalytic activity for H2-O2 PEMFCs.
RESUMEN
The oxygen evolution reaction (OER) is crucial for hydrogen production from water splitting and rechargeable metal-air batteries. However, the four-electron mechanism results in slow reaction kinetics, which needed to be accelerated by efficient catalysts. Herein, a hybrid catalyst of novel nickel-iron layered double hydroxide (NiFe LDH) on porous indium tin oxide (ITO) is presented to lower the overpotential of the OER. The as-prepared NiFe LDH@ITO catalyst showed superior catalytic activity toward the OER with an overpotential of only 240 mV at a current density of 10 mA/cm2. The catalyst also offered high stability with almost no activity decay after more than 200 h of chronopotentiometry test. Furthermore, the applications of NiFe LDH@ITO in (flexible) rechargeable zinc-air batteries exhibited a better performance than commercial RuO2 and can remain stable in cycling tests. It is supposed that the superior catalytic behavior originates from the ITO conductive framework, which prevents the agglomeration and facilitates the electron transfer during the OER process.
RESUMEN
Hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) have aroused great interest, but the high price of platinum group metals (PGMs) limits their development. The electronic reconstruction at the interface of a heterostructure is a promising strategy to enhance their catalytic performance. Here, MoO2/Ni heterostructure was synthesized to provide effective HER in an alkaline electrolyte and exhibit excellent HOR performance. Theoretical and experimental analyses prove that the electron density around the Ni atom is reduced. The electron density modulation optimizes the hydrogen adsorption and hydroxide adsorption free energy, which can effectively improve the activity of both HER and HOR. Accordingly, the prepared MoO2/Ni@NF catalyst reveals robust HER activity (η10 = 50.48 mV) and HOR activity (j0 = â¼1.21 mA cm-2). This work demonstrates an effective method to design heterostructure interfaces and tailor the surface electronic structure to improve HER/HOR performance.
RESUMEN
This study reports a high-performing nonprecious metal catalyst for the oxygen reduction reaction that is composed of highly dispersed Fe centered active sites on bamboolike carbon nanotubes. NH2-MIL-88B is used as the iron source and ZIF-8 as the carbon source. The precursors are uniformly mixed by ball milling, which destroys their crystal structures. A bamboolike carbon nanotube network results from the pyrolysis of the mixed precursors. The morphology is controlled by the proportion of the precursors and the pyrolysis temperature. The catalyst shows excellent oxygen reduction activity in both half-cell and full-cell tests. The onset potential and half-wave potential are 0.96 and 0.78 V vs RHE, respectively. In the fuel cell test, the current density reaches 0.85 A cm-2 at 0.7 V and 1.24 A cm-2 at 0.6 V (iR-corrected). The novel synthesis approach of the highly dispersed catalyst provides new strategy in the design of high effective nonprecious metal catalysts for fuel cell.
RESUMEN
A composite of FeOOH nanocubes anchored on carbon ribbons has been synthesized and used as a cathode material for Li/O2 batteries. Fe2+ ion-exchanged resin serves as a precursor for both FeOOH nanocubes and carbon ribbons, which are formed simultaneously. The as-prepared FeOOH cubes are proposed to have a core-shell structure, with FeOOH as the shell and Prussian blue as the core, based on information from XPS, TEM, and EDS mapping. As a cathode material for Li/O2 batteries, FeOOH delivers a specific capacity of 14816â mA h g-1 cathode with a cycling stability of 67 cycles over 400â h. The high performance is related to the low overpotential of the oxygen reduction/evolution reaction on FeOOH. The cube structure, the supporting carbon ribbons, and the -OOH moieties all contribute to the low overpotential. The discharge product Li2 O2 can be efficiently decomposed in the FeOOH cathode after a charging process, leading to higher cycling stability. Its high activity and stability make FeOOH a good candidate for use in non-aqueous Li/O2 batteries.
RESUMEN
A porous MoO2 nanosheet as an active and stable bifunctional electrocatalyst for overall water splitting, is presented. It needs a cell voltage of only about 1.53 V to achieve a current density of 10 mA cm(-2) and maintains its activity for at least 24 h in a two-electrode configuration.
