首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Proton exchange membrane water electrolyzer (PEMWE) is a green hydrogen production technology that can be coupled with intermittent power sources such as wind and photoelectric power. To achieve cost-effective operations, low noble metal loading on the anode catalyst layer is desired. In this study, a catalyst with RuO2 nanorods coated outside SnO2 nanocubes is designed, which forms continuous networks and provides high conductivity. This allows for the reduction of Ru contents in catalysts. Furthermore, the structure evolutions on the RuO2 surface are carefully investigated. The etched RuO2 surfaces are seen as the consequence of Co leaching, and theoretical calculations demonstrate that it is more effective in driving oxygen evolution. For electrochemical tests, the catalysts with 23 wt% Ru exhibit an overpotential of 178 mV at 10 mA cm−2, which is much higher than most state-of-art oxygen evolution catalysts. In a practical PEMWE, the noble metal Ru loading on the anode side is only 0.3 mg cm−2. The cell achieves 1.61 V at 1 A cm−2 and proper stability at 500 mA cm−2, demonstrating the effectiveness of the designed catalyst.  相似文献   

2.
Water electrolysis is an ideal method for industrial green hydrogen production. However, due to increasing scarcity of freshwater, it is inevitable to develop advanced catalysts for electrolyzing seawater especially at large current density. This work reports a unique Ru nanocrystal coupled amorphous-crystal Ni(Fe)P2 nanosheet bifunctional catalyst (Ru-Ni(Fe)P2/NF), caused by partial substitution of Fe to Ni atoms in Ni(Fe)P2, and explores its electrocatalytic mechanism by density functional theory (DFT) calculations. Owing to high electrical conductivity of crystalline phases, unsaturated coordination of amorphous phases, and couple of Ru species, Ru-Ni(Fe)P2/NF only requires overpotentials of 375/295 and 520/361 mV to drive a large current density of 1 A cm−2 for oxygen/hydrogen evolution reaction (OER/HER) in alkaline water/seawater, respectively, significantly outperforming commercial Pt/C/NF and RuO2/NF catalysts. In addition, it maintains stable performance at large current density of 1 A cm−2 and 600 mA cm−2 for 50 h in alkaline water and seawater, respectively. This work provides a new way for design of catalysts toward industrial-level seawater splitting.  相似文献   

3.
Alkaline membrane water electrolysis is a promising production technology, and advanced electrocatalyst and membrane electrode design have always been the core technology. Herein, an ion-exchange method and an environmentally friendly in situ green phosphating strategy are successively employed to fabricate Ru-Ru2P heterogeneous nanoparticles by using hydroxyapatite (HAP) as a phosphorus source, which is an exceptionally active electrocatalyst for hydrogen evolution reaction (HER). Density functional theory calculation results reveal that strong electronic redistribution occurs at the heterointerface of Ru-Ru2P, which modulates the electronic structure to achieve an optimized hydrogen adsorption strength. The obtained Ru-Ru2P possesses excellent HER performance (24 mV at 10 mA cm−2) and robust stability (1000 mA cm−2 for 120 h) in alkaline media. Furthermore, an environmentally friendly membrane electrode with a sandwich structure is assembled by HAP nanowires as an alkaline membrane, Ru-Ru2P as a cathodic catalyst, and NiFe-LDH as an anodic catalyst, respectively. The voltage of (−) Ru-Ru2P || NiFe-LDH/CNTs (+) (1.53 V at 10 mA cm−2) is lower than that of (−) 20 wt% Pt/C || RuO2 (+) (1.60 V at 10 mA cm−2) for overall water splitting. Overall, the studies not only design an efficient catalyst but also provide a new route to achieve a high-stability electrolyzer for industrial H2 production.  相似文献   

4.
Designing high‐performance, precious‐metal‐based, and economic electrocatalysts remains an important challenge in proton exchange membrane (PEM) electrolyzers. Here, a highly active and durable bifunctional electrocatalyst for PEM electrolyzers based on a rattle‐like catalyst comprising a Ni/Ru‐doped Pt core and a Pt/Ni‐doped RuO2 frame shell, which is topotactically transformed from an icosahedral Pt/Ni/Ru nanocrystal, is reported. The RuO2‐based frame shell with its highly reactive surfaces leads to a very high activity for the oxygen evolution reaction (OER) in acidic media, reaching a current density of 10 mA cm?2 at an overpotential of 239 mV, which surpasses those of previously reported catalysts. The Pt dopant in the RuO2 shell enables a sustained OER activity even after a 2000 cycles of an accelerated durability test. The Pt‐based core catalyzes the hydrogen evolution reaction with an excellent mass activity. A two‐electrode cell employing Pt/RuO2 as the electrode catalyst demonstrates very high activity and durability, outperforming the previously reported cell performances.  相似文献   

5.
Precise design of low-cost, efficient and definite electrocatalysts is the key to sustainable renewable energy. Herein, this work develops a targeted-anchored and subsequent spontaneous-redox strategy to synthesize nickel-iron layered double hydroxide (LDH) nanosheets anchored with monodispersed platinum (Pt) sites (Pt@LDH). Intermediate metal-organic frameworks (MOF)/LDH heterostructure not only provides numerous confine points to guarantee the stability of Pt sites, but also excites the spontaneous reduction for PtII. Electronic structure, charge transfer ability and reaction kinetics of Pt@LDH can be effectively facilitated by the monodispersed Pt moieties. As a result, the optimized Pt@LDH that with the 5% ultra-low content Pt exhibits the significant increment in electrochemical water splitting performance in alkaline media, which only afford low overpotentials of 58 mV at 10 mA cm−2 for hydrogen evolution reaction (HER) and 239 mV at 10 mA cm−2 for oxygen evolution reaction (OER), respectively. In a real device, Pt@LDH can drive an overall water-splitting at low cell voltage of 1.49 V at 10 mA cm−2, which can be superior to most reported similar LDH-based catalysts. Moreover, the versatility of the method is extended to other MOF precursors and noble metals for the design of ultrathin LDH supported monodispersed noble metal electrocatalysts promoting research interest in material design.  相似文献   

6.
Developing efficient and durable electrocatalysts for the oxygen evolution reaction (OER) in proton exchange membrane (PEM) electrolyzers represents a significant challenge. Herein, the cobalt-ruthenium oxide nano-heterostructures are successfully synthesized on carbon cloth (CoOx/RuOx-CC) for acidic OER through a simple and fast solution combustion strategy. The rapid oxidation process endows CoOx/RuOx-CC with abundant interfacial sites and defect structures, which enhances the number of active sites and the charge transfer at the electrolyte-catalyst interface, promoting the OER kinetics. Moreover, the electron supply effect of the CoOx support allows electrons to transfer from Co to Ru sites during the OER process, which is beneficial to alleviate the ion leaching and over-oxidation of Ru sites, improving the catalyst activity and stability. As a self-supported electrocatalyst, CoOx/RuOx-CC displays an ultralow overpotential of 180 mV at 10 mA cm−2 for OER. Notably, the PEM electrolyzer using CoOx/RuOx-CC as the anode can be operated at 100 mA cm−2 stably for 100 h. Mechanistic analysis shows that the strong catalyst-support interaction is beneficial to redistribute the electronic structure of Ru O bond to weaken its covalency, thereby optimizing the binding energy of OER intermediates and lowering the reaction energy barrier.  相似文献   

7.
Designing definite transition metal heterointerfaces is considered an effective strategy for the construction of efficient and robust oxygen evolution reaction (OER) electrocatalysts, but rather challenging. Herein, amorphous NiFe hydr(oxy)oxide nanosheet arrays (A-NiFe HNSAs) are grown in situ on the surface of a self-supporting Ni metal–organic frameworks (SNMs) electrode via a combination strategy of ion exchange and hydrolytic co-deposition for efficient and stable large-current-density water oxidation. The existence of the abundant metal–oxygen bonds on the heterointerfaces can not only be of great significance to alter the electronic structure and accelerate the reaction kinetics, but also enable the redistribution of Ni/Fe charge density to effectively control the adsorption behavior of important intermediates with a close to the optimal d-band center, dramatically narrowing the energy barriers of the OER rate-limiting steps. By optimizing the electrode structure, the A-NiFe HNSAs/SNMs-NF exhibits outstanding OER performance with small overpotentials of 223 and 251 mV at 100 and 500 mA cm−2, a low Tafel slope of 36.3 mV dec−1, and excellent durability during 120 h at 10 mA cm−2. This work significantly provides an avenue to understand and realize rationally designed heterointerface structures toward effective oxygen evolution in water-splitting applications.  相似文献   

8.
Developing efficient oxygen evolution reaction (OER) electrocatalysts for seawater electrolysis is still a big challenge. Herein, a facile one-pot approach is reported to synthesize RuO2-incorporated NiFe-metal organic framework (RuO2/NiFe-MOF) with unique nanobrick-nanosheet heterostructure as precatalyst. Driven by electric field, the RuO2/NiFe-MOF dynamically reconstructs into RuO2 nanoparticles-anchored NiFe oxy/hydroxide nanosheets (RuO2/NiFeOOH) with coherent interface, during which the dissolution and redeposition of RuO2 are witnessed. Owing to the synergistic interaction between RuO2 and NiFeOOH, the as-reconstructed RuO2/NiFeOOH exhibits outstanding alkaline OER activity with an ultralow overpotential of 187.6 mV at 10 mA cm−2 and a small Tafel slope of 31.9 mV dec−1 and excellent durability at high current densities of 840 and 1040 mA cm−2 in 1 m  potassium hydroxide (KOH). When evaluated for seawater oxidation, the RuO2/NiFeOOH only needs a low overpotential of 326.2 mV to achieve 500 mA cm−2 and can continuously catalyze OER at 500 mA cm−2 for 100 h with negligible activity degradation. Density function theory calculations reveal that the presence of strong interaction and enhanced charge transfer along the coherent interface between RuO2 and NiFeOOH ensures improved OER activity and stability.  相似文献   

9.
Exquisite design of RuO2-based catalysts to simultaneously improve activity and stability under harsh conditions and reduce the Ru dosage is crucial for advancing energy conversion involving oxygen evolution reaction (OER). Herein, a distinctive cobalt-doped RuOx framework is constructed on Co3O4 nanocones (Co3O4@CoRuOx) as a promising strategy to realize above urgent desires. Extensive experimental characterization and theoretical analysis demonstrate that cobalt doped in RuOx lattice brings the oxygen vacancies and lattice contraction, which jointly redistribute the electron configuration of RuOx. The optimized d-band center balances the adsorption energies of oxygenated intermediates, lowing the thermodynamical barrier of the rate-determining step; and meanwhile, the over-oxidation and dissolution of Ru species are restrained because of the p-band down-shifting of the lattice oxygen. Co3O4@CoRuOx with 3.7 wt.% Ru delivers the extremely low OER overpotentials at 10 mA cm−2 in alkaline (167 mV), neutral (229 mV), and acidic electrolytes (161 mV), and super operating stability over dozens of hours. The unprecedented activity ranks first in all pH-universal OER catalysts reported so far. These findings provide a route to produce robust low-loading Ru catalysts and an engineering approach for regulating the central active metal through synergy of co-existing defects to improve the catalytic performance and stability.  相似文献   

10.
The success in lowering the nucleation delay for Atomic Layer Deposition (ALD) of Ru on carbon surfaces is mitigated by constructive pretreatments resulting enhancement of C O functionality. Treatment of the carbon papers (CP) allowed Ru species deposition for minimum number of ALD cycles (25 cycles) with good conformality. The development of electrocatalysts from single atoms to nanoparticles (NPs) on conductive supports with low metal loadings, thus improving performance, is essential in electrocatalysis. For alkaline hydrogen evolution reaction, ALD decorated CPs with Ru exhibit low onset potentials of ≈4.7 mV versus reversable hydrogen electrode (RHE) (at 10 mA cm−2) and a high turnover frequency of 1.92 H2 s−1 at 30 mV versus RHE. The Ru decorated CPs show comparable to higher catalytic activity than of Platinum (Pt) decorated CP also developed by ALD. The current representation of unfamiliar catalytic activities of Ru active centers developed by ALD, pave a bright and sustainable path for energy conversion reactions.  相似文献   

11.
Rational design and development of highly efficient hydrogen evolution reaction (HER) electrocatalysts is of great significance for the development of green water electrolysis hydrogen production technology. Ru-engineered 1D PtCo-Ptrich nanowires (Ru-PtrichCo NWs) are fabricated by a facile electrodeposition method. The rich Pt surface on 1D Pt3Co contributes to the fully exposed active sites and enhanced intrinsic catalytic activity (co-engineered by Ru and Co atoms) for HER. The incorporation of Ru atoms can not only accelerate the water dissociation in alkaline condition to provide sufficient H* but also modulate the electronic structure of Pt to achieve optimized H* adsorption energy. As a result, Ru-PtrichCo NWs have exhibited ultralow HER overpotentials (η) of 8 and 112 mV to achieve current densities of 10 and 100 mA cm−2 in 1 m KOH, respectively, which far exceed those of commercial Pt/C catalyst (η10 = 29 mV, η100 = 206 mV). Density functional theory (DFT) calculations further demonstrate that the incorporated Ru atoms possess strong water adsorption capacity (−0.52 vs −0.12 eV for Pt), facilitating water dissociation. The Pt atoms in the outermost Pt-rich skin of Ru-PtrichCo NWs achieve optimized H* adsorption free energy (ΔGH*) of −0.08 eV, boosting hydrogen generation.  相似文献   

12.
Developing robust and highly active bifunctional electrocatalysts for overall water splitting is critical for efficient sustainable energy conversion. Herein, heteroatom-doped amorphous/crystalline ruthenium oxide-based hollow nanocages (M-ZnRuOx (MCo, Ni, Fe)) through delicate control of composition and structure is reported. Among as-synthesized M-ZnRuOx nanocages, Co-ZnRuOx nanocages deliver an ultralow overpotential of 17 mV at 10 mA cm−2 and a small Tafel slope of 21.61 mV dec−1 for hydrogen evolution reaction (HER), surpassing the commercial Pt/C catalyst, which benefits from the synergistic coupling effect between electron regulation induced by Co doping and amorphous/crystalline heterophase structure. Moreover, the incorporation of Co prevents Ru from over-oxidation under oxygen evolution reaction (OER) operation, realizing the leap from a monofunctional to multifunctional electrocatalyst and then Co-ZnRuOx nanocages exhibit remarkable OER catalytic activity as well as overall water splitting performance. Combining theory calculations with spectroscopy analysis reveal that Co is not only the optimal active site, increasing the number of exposed active sites while also boosting the long-term durability of catalyst by modulating the electronic structure of Ru atoms. This work opens a considerable avenue to design highly active and durable Ru-based electrocatalysts.  相似文献   

13.
RuO2 is considered as the state-of-the-art electrocatalyst for the oxygen evolution reaction (OER) in acidic media. However, its practical application is largely hindered by both the high reaction overpotential and severe electrochemical corrosion of the active centers. To overcome these limitations, innovative design strategies are necessary, which remains a great challenge. Herein, robust interface Ru centers between RuO2 and graphene, via a controllable oxidation of graphene encapsulating Ru nanoparticles, are presented to efficiently enhance both the activity and stability of the acidic OER. Through precisely controlling the reaction interface, a much lower OER overpotential of only 227 mV at 10 mA cm−2 in acidic electrolyte, compared with that of 290 mV for commercial RuO2, but a significantly higher durability than the commercial RuO2, are achieved. Density functional theory (DFT) calculations reveal that the interface Ru centers between the RuO2 and the graphene can break the classic scaling relationships between the free energies of HOO* and HO* to reduce the limiting potential, rendering an enhancement in the intrinsic OER activity and the resistance to over-oxidation and corrosion for RuO2.  相似文献   

14.
The development of trifunctional electrocatalyst for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) with deeply understanding the mechanism to enhance the electrochemical performance is still a challenging task. In this work, the distorted metastable hybrid-phase induced 1T′/1T Co,P SnS2 nanosheets on carbon cloth (1T′/1T Co,P SnS2@CC) is prepared and examined. The density functional theoretical (DFT) calculation suggests that the distorted 1T′/1T Co,P SnS2 can provide excellent conductivity and strong hydrogen adsorption ability. The electronic structure tuning and enhancement mechanism of electrochemical performance are investigated and discussed. The optimal 1T′/1T Co,P SnS2@CC catalyst exhibits low overpotential of ≈94 and 219.7 mV at 10 mA cm−2 for HER and OER, respectively. Remarkably, the catalyst exhibits exceptional ORR activity with small onset potential value (≈0.94 V) and half-wave potential (≈0.87 V). Most significantly, the 1T′/1T Co,P SnS2||Co,P SnS2 electrolyzer required small cell voltages of ≈1.53, 1.70, and 1.82 V at 10, 100, and 400 mA cm−2, respectively, which are better than those of state-of-the-art Pt-C||RuO2 (≈1.56 and 1.84 V at 10 and 100 mA cm−2). The present study suggests a new approach for the preparation of large-scalable, high performance hierarchical 3D next-generation trifunctional electrocatalysts.  相似文献   

15.
Exploring earth-abundant and highly efficient electrocatalysts is critical for further development of water electrolyzer systems. Integrating bifunctional catalytically active sites into one multi-component might greatly improve the overall water-splitting performance. In this work, amorphous NiO nanosheets coupled with ultrafine Ni and MoO3 nanoparticles (MoO3/Ni–NiO), which contains two heterostructures (i.e., Ni–NiO and MoO3–NiO), is fabricated via a novel sequential electrodeposition strategy. The as-synthesized MoO3/Ni–NiO composite exhibits superior electrocatalytic properties, affording low overpotentials of 62 mV at 10 mA cm−2 and 347 mV at 100 mA cm−2 for catalyzing the hydrogen and the oxygen evolution reaction (HER/OER), respectively. Moreover, the MoO3/Ni–NiO hybrid enables the overall alkaline water-splitting at a low cell voltage of 1.55 V to achieve 10 mA cm−2 with outstanding catalytic durability, significantly outperforming the noble-metal catalysts and many materials previously reported. Experimental and theoretical investigations collectively demonstrate the generated Ni–NiO and MoO3–NiO heterostructures significantly reduce the energetic barrier and act as catalytically active centers for selective HER and OER, synergistically accelerating the overall water-splitting process. This work helps to fundamentally understand the heterostructure-dependent mechanism, providing guidance for the rational design and oriented construction of hybrid nanomaterials for diverse catalytic processes.  相似文献   

16.
Developing a scalable approach to construct efficient and multifunctional electrodes for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) is an urgent need for overall water splitting and zinc–air batteries. In this work, a freestanding 3D heterostructure film is synthesized from a Ni-centered metal−organic framework (MOF)/graphene oxide. During the pyrolysis process, 1D carbon nanotubes formed from the MOF link with the 2D reduced graphene oxide sheets to stitch the 3D freestanding film. The results of the experiments and theoretical calculations show that the synergistic effect of the N-doped carbon shell and Ni nanoparticles leads to an optimized film with excellent electrocatalytic activity. Low overpotentials of 95 and 260 mV are merely needed for HER and OER, respectively, to reach a current density of 10 mA cm−2. In addition, a high half-wave potential of 0.875 V is obtained for the ORR, which is comparable to that of Pt/RuO2 and ranks among the top of non-noble-metal catalysts. The use of an “all-in-one” film as the electrode leads to excellent performance of the homemade water electrolyzer and zinc–air battery, indicating the potential of the film for practical applications.  相似文献   

17.
Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal–air batteries. Herein, a directional freeze-casting and annealing approach is reported for the construction of a 3D honeycomb nanostructured, N,P-doped carbon aerogel incorporating in situ grown FeP/Fe2O3 nanoparticles as the cathode in a flexible Zn–air battery (ZAB). The aqueous rechargeable Zn–air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g−1 at a current density of 20 mA cm−2 with a good long-term durability, outperforming those assembled with commercial Pt/C+RuO2 catalyst. Furthermore, such a foldable carbon aerogel with directional channels can serve as a freestanding air cathode for flexible solid-state Zn–air batteries without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mAh g−1 and an energy density of 517 Wh kg−1 at 5 mA cm−2 together with good cycling stability. This work offers a new strategy to design and synthesize highly effective bifunctional air cathodes to be applied in electrochemical energy devices.  相似文献   

18.
Heteroatom-doped transition metal-oxides of high oxygen evolution reaction (OER) activities interfaced with metals of low hydrogen adsorption energy barrier for efficient hydrogen evolution reaction (HER) when uniformly embedded in a conductive nitrogen-doped carbon (NC) matrix, can mitigate the low-conductivity and high-agglomeration of metal-nanoparticles in carbon matrix and enhances their bifunctional activities. Thus, a 3D mesoporous heterostructure of boron (B)-doped cobalt-oxide/cobalt-metal nanohybrids embedded in NC and grown on a Ni foam substrate (B-CoO/Co@NC/NF) is developed as a binder-free bifunctional electrocatalyst for alkaline water-splitting via a post-synthetic modification of the metal–organic framework and subsequent annealing in different Ar/H2 gas ratios. B-CoO/Co@NC/NF prepared using 10% H2 gas (B-CoO/Co@NC/NF [10% H2]) shows the lowest HER overpotential (196 mV) and B-CoO/Co@NC/NF (Ar), developed in Ar, shows an OER overpotential of 307 mV at 10 mA cm−2 with excellent long-term durability for 100 h. The best anode and cathode electrocatalyst-based electrolyzer (B-CoO/Co@NC/NF (Ar)(+)//B-CoO/Co@NC/NF (10% H2)(−)) generates a current density of 10 mA cm−2 with only 1.62 V with long-term stability. Further, density functional theory investigations demonstrate the effect of B-doping on electronic structure and reaction mechanism of the electrocatalysts for optimal interaction with reaction intermediates for efficient alkaline water-splitting which corroborates the experimental results.  相似文献   

19.
Electrocatalytic oxidation of urea (UOR) is a potential energy-saving hydrogen production technology that can replace oxygen evolution reaction (OER). Therefore, CoSeP/CoP interface catalyst is synthesized on nickel foam using hydrothermal, solvothermal, and in situ template methods. The strong interaction of tailored CoSeP/CoP interface promotes the hydrogen production performance of electrolytic urea. During the hydrogen evolution reaction (HER), the overpotential can reach 33.7 mV at 10 mA cm−2. The cell voltage can reach 1.36 V at 10 mA cm−2 in the overall urea electrolytic process. Notably, the overall urine electrolysis performance of the catalyst in the human urine medium can reach 1.40 V at 10 mA cm−2 and can exhibit durable cycle stability at 100 mA cm−2. Density functional theory (DFT) proves that the CoSeP/CoP interface catalyst can better adsorb and stabilize reaction intermediates CO* and NH* on its surface through a strong synergistic effect, thus enhancing the catalytic activity.  相似文献   

20.
It is not enough to develop an ideal hydrogen evolution reaction (HER) electrocatalysts by single strategy. Here, the HER performances are significantly improved by the combined strategies of P and Se binary vacancies and heterostructure engineering, which is rarely explored and remain unclear. As a result, the overpotentials of MoP/MoSe2-H heterostructures rich in P and Se binary vacancies are 47 and 110 mV at 10 mA cm−2 in 1 m KOH and 0.5 m H2SO4 electrolytes, respectively. Especially, in 1 m KOH, the overpotential of MoP/MoSe2-H is very close to commercial Pt/C at the beginning and even better than Pt/C when current density is over 70 mA cm−2. The strong interactions between MoSe2 and MoP facilitate electrons transfer from P to Se. Thus, MoP/MoSe2-H possesses more electrochemically active sites and faster charge transfer capability, which are all in favor of high HER activities. Additionally, Zn-H2O battery with MoP/MoSe2-H as cathode is fabricated for simultaneous generation of hydrogen and electricity, which displays the maximum power density of up to 28.1 mW cm−2 and stable discharging performance for 125 h. Overall, this work validates a vigorous strategy and provides guidance for the development of efficient HER electrocatalysts.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号