ABSTRACT
The acceleration of active sites formation through surface reconstruction is widely acknowledged as the crucial factor in developing high-performance oxygen evolution reaction (OER) catalysts for water splitting. Herein, a simple one-step corrosion method and magnesium (Mg)-promoted strategy are reported to develop the NiFe-based catalyst with enhanced OER performance. The Mg is introduced in NiFe materials to preparate a "pre-catalyst" Mg-Ni/Fe2O3. In-situ Raman shows that Mg doping would accelerate the self-reconstruction of Ni/Fe2O3 to form active NiOOH species during OER. In-situ infrared indicates that Mg doping benefits the formation of *OOH intermediate. Theoretical analysis further confirms that Mg doping can optimize the adsorption of oxygen intermediates, accelerating the OER kinetics. Accordingly, the Mg-Ni/Fe2O3 catalyst exhibits excellent OER performance with overpotential of 168 mV at 10 mA cm-2. The anion exchange membrane water electrolyzer achieved 200 mA cm-2 at voltage of 1.53 V, showing excellent stability over 500 h as well. This work demonstrates the potential of Mg-promoted strategy in regulating the activity of transition metal-based OER electrocatalysts.
ABSTRACT
Nickel anchored N-doped carbon electrocatalysts (Ni-N-C) are rapidly developed for the electrochemical reduction reaction of carbon dioxide (CO2RR). However, the high-performanced Ni-N-C analogues design for CO2RR remains bewilderment, for the reason lacking of definite guidance for its structure-activity relationship. Herein, the correlation between the proportion of nitrogen species derived from various nitrogen sources and the CO2RR activity of Ni-N-C is investigated. The x-ray photoelectron spectroscopy (XPS) spectrum combined with the CO2RR performance results show that pyridinic-N content has a positive correlation with CO2RR activity. Moreover, density functional theory (DFT) demonstrates that pyridinic-N coordinated Ni-N4sites offers optimized free energy and favorable selectivity towards CO2RR compared with pyrrolic-N. Accordingly, Ni-Na-C with highest pyridinic-N content (ammonia as nitrogen source) performs superior CO2RR activity, with the maximum carbon monoxide faradaic efficiency (FECO) of 99.8% at -0.88 V vs. RHE and the FECOsurpassing 95% within potential ranging of -0.88 to -1.38 V vs. RHE. The building of this parameter for CO2RR activity of Ni-N-C give instructive forecast for low-cost and highly active CO2RR electrocatalysts.
ABSTRACT
It is critical and challenging to develop highly active and low cost bifunctional electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) in water electrolysis. Herein, we propose cerium-vanadium-based hollow nanopillar arrays supported on nickel foam (CeV-HNA/NF) as bifunctional HER/OER electrocatalysts, which are prepared by etching the V metal-organic framework with Ce salt and then pyrolyzing. Etching results in multidimensional optimizations of electrocatalysts, covering substantial oxygen vacancies, optimized electronic configurations, and an open-type structure of hollow nanopillar arrays, which contribute to accelerating the charge transfer rate, regulating the adsorption energy of H/O-containing reaction intermediates, and fully exposing the active sites. The reconstruction of the electrocatalyst is also accelerated by Ce doping, which results in highly active hydroxy vanadium oxide interfaces. Therefore, extremely low overpotentials of 170 and 240 mV under a current density of 100 mA cm-2 are achieved for the HER and OER under alkaline conditions, respectively, with long-term stability for 300 h. An electrolysis cell with CeV-HNA/NF as both the cathode and anode delivers a small voltage of 1.53 V to achieve water electrolysis under 10 mA cm-2, accompanied by superior durability for 150 h. This design provides an innovative way to develop advanced bifunctional electrocatalysts for overall water electrolysis.
ABSTRACT
In this work, we have analyzed the neuroprotective activity of marrubiin against MPTP-induced Parkinson's disease (PD) in rat brains. MPTP (1-methyl-4-phenyl-1, 2, 3, 6-tetrahydropyridine) a neurotoxin was administered intraperitoneally (i.p.,) to rats and then treated using marrubiin. After marrubiin treatment, rats were trained, and tested for behavioral analyses like cognitive performance, open field test, rotarod test, grip strength test, beam walking test, the status of body weight, and striatal levels of neurotransmitters like dopamine, norepinephrine, serotonin, DOPAC, homovanillic acid, 5-hydroxy indole acetic acid, the status of oxidative stress markers like LPO, protein carbonyl content (PCC), Xanthine oxidase (XO), and status of antioxidant enzyme levels like SOD, CAT, GPX in the striatum and hippocampal tissues, status of neuroinflammatory markers like TNF-α, IL1ß, IL-6, and status of histological architecture in brain striatum were also analyzed. All these parameters were significantly (p < 0.05) abnormal in MPTP-induced rats. Marrubiin (MB) treated shows significant (p < 0.05) near normal behavioral restoration in cognitive performance, open field, rotarod, grip strength, and beam walking tests. Furthermore, the status of body weight, and levels of neurotransmitters, were also significantly (p < 0.05) reversed to near normalcy in marrubiin-treated rats. Similarly, oxidative stress, antioxidant enzyme levels in the striatum and hippocampal tissues, TNF-α, IL1ß, IL-6 levels, and histological architecture were noted to be restored to near normalcy in marrubiin-treated rats. Collectively, our preliminary results highlight the neuroprotective ability of marrubiin. However, the cellular and biochemical mechanisms of marrubiin's neuroprotective ability have to be studied in detail.
ABSTRACT
Earth-abundant metal oxides are usually considered as stable but catalytically inert toward hydrogen evolution reaction (HER) due to their unfavorable hydrogen intermediate adsorption performance. Herein, a heavy rare earth (Y) and transition metal (Co) dual-doping induced lattice strain and oxygen vacancy stabilization strategy is proposed to boost CeO2 toward robust alkaline HER. The induced lattice compression and increased oxygen vacancy (Ov) concentration in CeO2 synergistically improve the water dissociation on Ov sites and sequential hydrogen adsorption at activated Ov-neighboring sites, leading to significantly enhanced HER kinetics. Meanwhile, Y doping offers stabilization effect on Ov by its stronger YâO bonding over CeâO, which endows the catalyst with excellent stability. The Y,Co-CeO2 electrocatalyst exhibits an ultra-low HER overpotential (27 mV at 10 mA cm-2) and Tafel slope (48 mV dec-1), outperforming the benchmark Pt electrocatalyst. Moreover, the anion exchange membrane water electrolyzer incorporated with Y,Co-CeO2 achieves excellent stability of 500 h under 600 mA cm-2. This synergistic lattice strain and oxygen vacancy stabilization strategy sheds new light on the rational development of efficient and stable oxide-based HER electrocatalysts.
ABSTRACT
Oxygen evolution reaction (OER) plays a key role in electrochemical conversion, which needs efficient and economical electrocatalyst to boost its kinetics for large-scale application. Herein, a bimetallic CoP/FeP2heterostructure with a three-dimensional ordered macroporous structure (3DOM-CoP/FeP2) was synthesized as an OER catalyst to demonstrate a heterogeneous engineering induction strategy. By adjusting the electron distribution and producing a lot of active sites, the heterogeneous interface enhances catalytic performance. High specific surface area is provided by the 3DOM structure. Additionally, at the solid-gas-electrolyte threephase interface, the electrocatalytic reaction exhibits good mass transfer.In situRaman spectroscopy characterization revealed that FeOOH and CoOOH reconstructed from CoP/FeP2were the true OER active sites. Consequently, the 3DOM-CoP/FeP2demonstrates superior OER activity with a low overpotentials of 300/420 mV at 10/100 mA cm-2and meritorious OER durability. It also reveals promising performance as the overall water splitting anode.
ABSTRACT
The development of highly active and durable nonprecious metal-based bifunctional electrocatalysts for oxygen reduction/evolution reaction (ORR/OER) is important for rechargeable zinc-air batteries. Herein, a three-dimensional conductive niobium-doped TiO-TiO2 heterostructure supported ZIF-67-derived Co-NC bifunctional catalyst was fabricated. In the Co-NC@Nb-TiOx catalyst, the Nb doping promoted the formation of TiO-TiO2 heterojunction support, enhanced its conductivity and stability and provided strong electron metal-support interaction between Co-NC and Nb-TiOx. Also, the supported Co-NC nanoparticles provided abundant active sites with excellent ORR/OER activity. Experimental analysis reveals that the high OER activity of Co-NC@Nb-TiOx can be attributed to the in-situ generated CoOOH species. It exhibits excellent ORR activity, as shown by its onset potential (0.95 V vs. RHE) and half-wave potential (0.86 V vs. RHE). Its OER overpotential at 10 mA cm-2 is 480 mV. The zinc-air battery realizes outstanding cycling stability over 225 h cycles tested at 10 mA cm-2. This work demonstrates the importance of designing highly stable metal oxide-supported catalysts in electrochemical energy conversion devices.
ABSTRACT
Active and stable electrocatalysts toward oxygen evolution reaction (OER) are essential for alkaline water splitting. Herein, an efficient and durable high-valence NiFe-based OER electrocatalyst is developed, featuring a protective CeO2- x coating to prevent the corrosion of carbon substrates during oxidative OER operation, ensuring excellent catalyst stability. The incorporation of a CeO2- x coating also leads to the formation of a Ce-doped NiFe sulfide catalyst. The Ce modulator enables the dynamic transformation of NiFe sulfide into highly active (oxy)hydroxide species with high-valence Ni sites and enhanced NiâO covalency, thereby improving its OER catalytic activity. Accordingly, the prepared NiFeS2 /CeO2- x /CC catalyst achieves enhanced OER activity with an overpotential of 260 mV at 100 mA cm-2 in 1.0 m KOH. Moreover, the catalyst achieves 100 mA cm-2 current density at an overpotential of 187 mV for the hydrogen evolution reaction. The anion exchange membrane water electrolyzer reached 500 mA cm-2 at 1.73 V cell voltage with excellent stability for 500 h continuous operation. This study demonstrates a promising approach for the fabrication of robust water-splitting electrocatalysts.
ABSTRACT
The development of low cost efficient catalysts for oxygen evolution reaction (OER) is still a obstacle to realize the commercialization of electrocatalytic water splitting. Herein, interface engineering and heteroatom doping is adopted to synthesize iron and vanadium doped nickel sulfide on nickel foam via hydrothermal method followed by hydrogen treatment to create sulfur defects. The optimized nanoflower-like FeVNi3S2-x/NF is an efficient OER electrocatalyst that outperforms many of the reported transition metals catalysts. Benefiting from abundant sulfur defects and the synergistic effect of heteroatom doping, FeVNi3S2-x/NF exhibits an ultralow overpotential of 230 mV to reach a current density of 100 mA cm-2, a rapid reaction kinetics with a small Tafel slope of 46.6 mV dec-1, and a stable long-term durability in 1 M KOH. Experimental results and characterizations confirm that sulfur vacancies together with the synergistic effect from multiple heteroatom doping can effectively regulate the electronic structure, resulting in increased electrical conductivity and electrochemically active surface area, thus enhancing OER performance. Furthermore,in situRaman spectroscopy reveals that, the reconstitution amorphous nickel oxyhydroxide (NiOOH) on the catalyst surface is responsible for catalyzing the OER reaction. This work represents a promising methodology to synthesize low-cost and highly active OER electrocatalysts.
ABSTRACT
As an attractive high-energy-density technology, the practical application of lithium-sulfur (Li-S) batteries is severely limited by the notorious dissolution and shuttle effect of lithium polysulfides (LiPS), resulting in sluggish reaction kinetics and uncontrollable dendritic Li growth. Herein, a p-n typed heterostructure consisting of n-type MoS2 nanoflowers embedded with p-type NiO nanoparticles is designed on carbon nanofibers (denoted as NiO-MoS2 @CNFs) as both cathode sulfur immobilizer and anode Li stabilizer for practical Li-S batteries. Such p-n typed heterostructure is proposed to establish the built-in electric field across the heterointerface for facilitated the positive charge to reach the surface of NiO-MoS2 , meanwhile inherits the excellent LiPS adsorption ability of p-type NiO nanoparticles and catalytic ability of n-type MoS2 . As the anode matrix, the implementation of NiO-MoS2 heterostructure can prevent the growth of Li dendrites by enhancing the lithiophilicity and reducing local current density. The obtained Li-S full battery exhibits an ultra-high areal capacity over 7.3 mAh cm-2 , far exceeding that of current commercial Li-ion batteries. Meanwhile, a stable cycling performance can be achieved under low electrolyte/sulfur ratio of 5.8 µL mg-1 and negative/positive capacity ratio of 1. The corresponding pouch cell maintains high energy density of 305 Wh kg-1 and stable cycling performance under various bending angles.
ABSTRACT
In this study, oxidation-resistive deficient TiO2-x supported NiFe-based electrocatalysts were developed towards efficient and durable water splitting performance. The oxidation-resistive deficient TiO2-x support with oxygen vacancies ensures good stability and electrical conductivity of the catalyst. The decorated NiFe and NiFeP nanosheets serve as efficient catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. In 1 M KOH, the NiFe@TiO2-x and NiFeP@TiO2-x electrodes show low overpotential for OER (300 mV) and HER (273 mV) at 100 mA cm-2, respectively, and excellent stability performance in overall water splitting as well. In-situ Raman and theoretical analysis reveals that the in-situ formed Fe3+-doped NiOOH species are essential in catalyzing OER on NiFe@TiO2-x, particularly the electron localization of surface Fe-O bonds offers lower energy barriers for OER elemental reactions and thus enhance its catalytic activity. This work provides an oxide-based catalyst support strategy for the development of stable and active overall water splitting catalysts, and advances the insights on catalytic origin of NiFe-based catalysts as well.
ABSTRACT
The practical application of lithium-sulfur batteries (LSBs) is still hindered by the shuttle effect of lithium polysulfides (LiPS) and slow sulfur conversion kinetics. Herein, a LiPS inhibited covalent organic framework (COF)-coated conductive porous metal oxide design strategy is proposed towards the development of efficient and durable sulfur cathode in LSBs. This strategy is demonstrated by coating a TpPa-1 COF layer on cobalt-decorated titanium oxynirtide (TiOxNy) with a three-dimensional ordered microporous framework (3DOM) structure. In this strategy, the oxygen-deficient TiOxNy framework ensures a good conductivity and structural stability of the cathode during the charge/discharge process. The 3DOM macrospores provide a high capacity for sulfur accommodation and exposes active interfaces, whereas the coated TpPa-1 COF featured with ultrafine microspore offer an effective confinement of LiPS within the 3DOM framework, mitigating its shuttling effect. At the same time, the Co embedded in 3DOM TiOxNy servers as efficient catalyst promoting the sulfur electrochemical reaction. Attributed to these structural superiorities, the 3DOM TpPa-1@Co/TiOxNy/S cathode exhibits excellent performance even under high sulfur loading and low electrolyte condition. This work of using microporous COF coating with conductive macroporous metal oxides offers an effective alternative strategy for the design of practical sulfur battery.
ABSTRACT
Visible-light-responsive bismuth-based oxyhalide has recently attracted extensive attention, however, the promotion of its charge separation is still challenging. Herein, we introduce iodine into Bi2 GdO4 Cl to synthetize I-doped Bi2 GdO4 Cl (denoted as yI-Bi2 GdO4 Cl, 0≤y≤2). The incorporation of I- ions is found to enhance light absorption and to accelerate charge separation by combining various characterizations such as density functional theory calculation, photoelectrochemical test, electrochemical impedance spectroscopy, photoluminescence spectrum, and open-circuit voltage decay. The O2 -evolving performances of 1I-Bi2 GdO4 Cl with optimized dopant concentration of I- ion and IrO2 loaded 1I-Bi2 GdO4 Cl are tremendously enhanced by ca. 4 and 45â times compared to pristine Bi2 GdO4 Cl. Notably, The O2 evolution rate reaches as high as 154.8â µmol â h-1 with an apparent quantum efficiency of â¼1.1 % at 420â nm. The synthetic iodine-doped photocatalyst remains stable after long-term photoreaction, demonstrating its potential in the field of photocatalysis.
ABSTRACT
Non-precious and stable electrocatalysts towards both oxygen and hydrogen evolution reaction (OER/HER) are essential for effective overall water splitting in alkaline solution. In this study, a sulfur defective and manganese-doped nickel sulfide nanosheet that uniformly grown on nickel foam substrate (Mn-Ni3S2-x@NF) is synthesized. In alkaline solution, the Mn-Ni3S2-x@NF showed a low overpotential of 76 and 110 mV for OER and HER at 10 mA cm-2, respectively, together exhibiting excellent stability for both OER and HER reaction. It was confirmed by the experimental results that sulfur defects and Mn-doping synergistically optimized the electronic structure of Mn-Ni3S2-xwith increased electrical conductivity and enhanced OER/HER activity. Moreover, amorphous nickel oxyhydroxide (NiOOH) was observed byin situRaman during the OER condition, suggesting NiOOH is the active phase for OER reaction. Furthermore, the electrolyzer assembled by Mn-Ni3S2-x@NF merely needs 1.46 V to reach 10 mA cm-2and shows good stability as well. This study provides a feasible way to prepare high-efficiency bifunctional catalysts for overall water splitting.
ABSTRACT
The shuttle effect and slow redox kinetics of sulfur cathode are the most significant technical challenges to the practical application of lithium-sulfur (Li-S) battery. Herein, a novel zwitterionic covalent organic framework (ZW-COF) wrapped onto carbon nanotubes (CNTs), labeled as ZW-COF@CNT, is developed by a reversible condensation reaction of 1,3,5-benzenetricarboxaldehyde (BTA) and 3,8-diamino-6-phenylphenanthridine (DPPD) with CNTs as a template and a subsequently-one-step post-synthetic grafting reaction with 1,3-propanesultone. The experimental results showed that, after loading active material sulfur, zwitterionic ZW-COF@CNT can effectively suppress the shuttle effect of the soluble lithium polysulfides (LiPSs) in Li-S batteries, and exhibits better cycling behavior than the as-developed neutral COF@CNT. Specifically, the as-obtained ZW-COF@CNT based sulfur cathode can maintain a discharge capacity of 944 mAh/g after 100 cycles, while that of COF@CNT based sulfur cathode drops to (665 mAh/g) after 100 cycles. Moreover, the ZW-COF@CNT based sulfur cathode delivers an attractive prolonged cycling behavior with a low capacity decay rate of 0.046 % per cycle at 1 C. This work sheds new light on rational selection and design of functionalized COFs based sulfur cathode in the Li-S battery.
ABSTRACT
Development of efficient lithium-sulfur (Li-S) battery requires the need to develop an appropriate functional separator that allows strong facilitation and transport of lithium ions together with limited passage of polysulfides. In this work, a multifunctional separator (TB-BAA/SWCNT/PP) is developed through spin coating of a novel zwitterionic microporous polymer (TB-BAA) on the gutter layer constructed from single-walled carbon nanotubes (SWCNT), where commercially available polypropylene (PP) separator is used to act as the mechanical support. SWCNT in this study serves as the first modification layer to decrease the size of the macropores in the PP separator, while the ultrathin TB-BAA top barrier layer with the presence of zwitterionic side chains allows the creation of confined ionic channels with both lithiophilic and sulfophilic groups. Due to the presence of available chemical interactions with lithium polysulfides, selective ion transport can be foreseen through such separator. In this regard, shuttle effect that is frequently encountered in Li-S battery can be suppressed effectively via implementing the as-obtained functional separator, resulting in the creation of credible and stable sulfur electrochemistry. The TB-BAA/SWCNT/PP-based Li-S battery has been investigated to possess high cycling ability (capacity fading per cycle of 0.055% over 500 cycles at 1 C) together with decent rate capability (736.6 mAh g-1 at 3 C). In addition, a high areal capacity retention of 5.03 mAh cm-2 after 50 cycles can be also obtained under raised sulfur loading (5.4 mg cm-2).
ABSTRACT
It is of significant importance to suppress the polysulfide shuttle effect for the commercial application of lithium-sulfur batteries. Herein, continuous MIL-101(Cr) membranes were successfully fabricated on carbon nanotube films utilizing a simplein situgrowth method, aiming at constructing interlayer materials for inhibiting the shuttle effect. Owing to the suitable pore aperture and super electrolyte wettability, the as-developed MIL-101(Cr) membrane can effectively inhibit the shuttle behaviour of polysulfides while allowing the fast transport of Li-ions simultaneously, working as an ionic sieve. Additionally, this MOFs membrane is also helpful in accelerating the polysulfide catalytic conversion. Therefore, the proposed interlayer delivers an extraordinary rate capability, showing a remarkable capacity of 661.9 mAh g-1under 5 C. Meanwhile, it also exhibits a high initial capacity of 816.1 mAh g-1at 1 C and an exceptional durability with an extremely low capacity fading of 0.046% per cycle over 500 cycles.
ABSTRACT
It is of significant importance to suppress the polysulfide shuttle effect for the commercial application of lithium-sulfur batteries. Herein, continuous MIL-101(Cr) membranes were successfully fabricated on carbon nanotube films utilizing a simple in-situ growth method, aiming at constructing interlayer materials for inhibiting the shuttle effect. Owing to the suitable pore aperture and super electrolyte wettability, the as-developed MIL-101(Cr) membrane can effectively inhibit the shuttle behaviour of polysulfides while allowing the fast transport of Li-ions simultaneously, working as an ionic sieve. Additionally, this MOFs membrane is also helpful in accelerating the polysulfide catalytic conversion. Therefore, the proposed interlayer delivers an extraordinary rate capability, showing a remarkable capacity of 661.9 mAh g-1 under 5 C. Meanwhile, it also exhibits a high initial capacity of 816.1 mAh g-1 at 1 C and an exceptional durability with an extremely low capacity fading of 0.046 % per cycle over 500 cycles.
ABSTRACT
Developing efficient and stable multifunctional electrocatalyst is very important for zinc-air batteries in practical. Herein, semiconductive spinel CuFe2O4supported Co-N co-doped carbon (Co-NC) and CoFe alloy nanoparticles were proposed. In this strategy, the three-dimensional ordered macroporous CuFe2O4support provides rich channels for mass transmission, revealling good corrosion-resistance and durability at the same time. ZIF-67 derived Co-NC decoration improves the conductivity of the catalyst. Further, the uniformly distributed Co-NC and CoFe nanoparticles (C/CF) dramatically promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance. Accordingly, C/CF@CuFe2O4catalyst shows remarkable bifunctional electrocatalytic activity, with an ORR half-wave potential of 0.86 V, and an OER over-potential of 0.46 V at 10 mA cm-2. The zinc-air battery using this catalyst exhibits a power density of 95.5 mW cm-2and a durable cyclability for over 170 h at a current density of 10 mA cm-2, which implies a great potential in practical application.
ABSTRACT
Rational design of metal oxide supported non-precious metals is essential for the development of stable and high-efficiency oxygen reduction reaction (ORR) electrocatalysts. Here, an efficient ORR catalyst consisting of binary Fe/Co nanoclusters supported by defective tungsten oxide and embedded N-doped carbon layer (NC) with a 3D ordered macroporous architecture (3DOM Fe/Co@NC-WO2- x ) is developed. The oxygen deficient 3DOM WO2- x not only serves as a porous and stable support, but also enhances the conductivity and ensures good dispersion of the binary Fe/Co nanocluster, benefiting its ORR catalytic activity. Theoretical calculation shows that there exists a synergistic effect of electron transfer from Fe to Co in the supported binary Fe/Co cluster, promoting the ORR reaction energetics. Accordingly, the 3DOM Fe/Co@NC-WO2- x catalyst exhibits excellent ORR activity in alkaline medium with a half wave potential (E1/2 ) of 0.87 V higher than that of Pt/C (0.85 V). The zinc-air batteries assembled by 3DOM Fe/Co@NC-WO2- x cathode deliver a higher power density and specific capacity than that of Pt/C. A new strategy of combining synergistic binary-metal nanoclusters and conductive metal oxide support design is provided here to develop efficient and durable ORR electrocatalyst.