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1.
Tantalum nitride (Ta3N5) with a suitable bandgap (≈2 eV) is regarded as one of the most promising photocatalysts for efficient solar energy harvesting and conversion. However, Ta3N5 suffers from low hydrogen production activity due to the low carrier mobility and fast carrier recombination. Thus, the design of Ta3N5 nanostructures to facilitate charge carrier transport and improve photocatalytic performance remains a challenge. This study reports a new type of ultrathin (≈2 nm) Ta3N5 nanomesh with high specific surface area (284.6 m2 g?1) and excellent crystallinity by an innovative bottom‐up graphene oxide templated strategy. The resulting Ta3N5 nanomeshes demonstrate drastically improved electron transport ability and prolonged lifetime of charge carriers, due to the nature of high surface area and excellent crystallinity. As a result, when used as photocatalysts, the Ta3N5 nanomeshes exhibit a greater than tenfold improvement in solar hydrogen production compared to bulk counterparts. This work provides an effective and generic strategy for designing 2D ultrathin nanomesh structures for nonlayered materials with improved catalytic activity.  相似文献   

2.
Earth‐abundant amorphous nanomaterials with rich structural defects are promising alternative catalysts to noble metals for an efficient electrochemical oxygen evolution reaction; however, their inferior electrical conductivity and poor morphological control during synthesis hamper the full realization of their potency in electrocatalysis. Herein, a rapid surface‐guided synthetic approach is proposed to introduce amorphous and mixed‐metal oxyhydroxide overlayers on ultrathin Ni‐doped MnO2 (Ni? MnO2) nanosheet arrays via a galvanic replacement mechanism. This method results in a monolithic 3D porous catalyst with a small overpotential of only 232 mV to achieve a current density of 10 mA cm?2 in 1 m KOH, which is much lower than the corresponding value of 307 mV for the Ni? MnO2 reference sample. Detailed structural and electrochemical characterization reveal that the unique Ni? MnO2 ultrathin nanosheet arrays do not only provide a large surface area to guide the formation of active amorphous catalyst layers but also ensure the effective charge transport owing to their high electron conductivity, collectively contributing to the greatly improved catalyst activity. It is envisioned that this highly operable surface‐guide synthetic strategy may open up new avenues for the design and fabrication of novel 3D nanoarchitectures integrated with functional amorphous materials for broadened ranges of applications.  相似文献   

3.
High energy density at high power density is still a challenge for the current Li‐ion capacitors (LICs) due to the mismatch of charge‐storage capacity and electrode kinetics between capacitor‐type cathode and battery‐type anode. In this work, B and N dual‐doped 3D porous carbon nanofibers are prepared through a facile method as both capacitor‐type cathode and battery‐type anode for LICs. The B and N dual doping has profound effect in tuning the porosity, functional groups, and electrical conductivity for the porous carbon nanofibers. With rational design, the developed B and N dual‐doped carbon nanofibers (BNC) exhibit greatly improved electrochemical performance as both cathode and anode for LICs, which greatly alleviates the mismatch between the two electrodes. For the first time, a 4.5 V “dual carbon” BNC//BNC LIC device is constructed and demonstrated, exhibiting outstanding energy density and power capability compared to previously reported LICs with other configurations. In specific, the present BNC//BNC LIC device can deliver a large energy density of 220 W h kg?1 and a high power density of 22.5 kW kg?1 (at 104 W h kg?1) with reasonably good cycling stability (≈81% retention after 5000 cycles).  相似文献   

4.
A significant advance toward the design and fabrication of a novel hierarchical supercapacitor electrode consisting of FeCo2S4‐tubes with well‐defined square cross‐section and intersecting nanosheets built porous shells on a 3D porous Ni backbone via controlled sulfidation is reported. This general method allows template‐free synthesis of metal sulfides tubular structures with polygonal cross‐sections and also fine control over the nanostructure leading to both maximized porosity and saturation sulfidation. New insights into concentration and time dependent sulfidation reaction kinetics are proposed. The FeCo2S4 electrode achieves a specific capacitance reaching 2411 F g‐1 at 5 mA cm‐2 and good rate capability, which are superior over those for nanotube arrays of other ternary transition metal sulfides. This is attributed to rich redox reactions, the highly porous but robust architecture as well as high electrical conductivity. Especially such porous shells effectively avoid “dead volume”, thus improve the utilization ratio of the electrode material. Asymmetric solid‐state device applying the FeCo2S4 as positive electrode and N‐doped graphene hydrogel film as negative electrode has a high cell voltage of 1.6 V and thus delivers considerably higher energy density of 76.1 W h kg‐1 (at 755 W kg‐1) than those reported for similar devices.  相似文献   

5.
As the lightest member of transition metal dichalcogenides, 2D titanium disulfide (2D TiS2) nanosheets are attractive for energy storage and conversion. However, reliable and controllable synthesis of single‐ to few‐layered TiS2 nanosheets is challenging due to the strong tendency of stacking and oxidation of ultrathin TiS2 nanosheets. This study reports for the first time the successful conversion of Ti3C2Tx MXene to sandwich‐like ultrathin TiS2 nanosheets confined by N, S co‐doped porous carbon (TiS2@NSC) via an in situ polydopamine‐assisted sulfuration process. When used as a sulfur host in lithium–sulfur batteries, TiS2@NSC shows both high trapping capability for lithium polysulfides (LiPSs), and remarkable electrocatalytic activity for LiPSs reduction and lithium sulfide oxidation. A freestanding sulfur cathode integrating TiS2@NSC with cotton‐derived carbon fibers delivers a high areal capacity of 5.9 mAh cm?2 after 100 cycles at 0.1 C with a low electrolyte/sulfur ratio and a high sulfur loading of 7.7 mg cm?2, placing TiS2@NSC one of the best LiPSs adsorbents and sulfur conversion catalysts reported to date. The developed nanospace‐confined strategy will shed light on the rational design and structural engineering of metal sulfides based nanoarchitectures for diverse applications.  相似文献   

6.
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   

7.
Practical applications of room temperature sodium–sulfur batteries are still inhibited by the poor conductivity and slow reaction kinetics of sulfur, and dissolution of intermediate polysulfides in the commonly used electrolytes. To address these issues, starting from a novel 3D Zn‐based metal–organic framework with 2,5‐thiophenedicarboxylic acid and 1,4‐bis(pyrid‐4‐yl) benzene as ligands, a S, N‐doped porous carbon host with 3D tubular holes for sulfur storage is fabricated. In contrast to the commonly used melt‐diffusion method to confine sulfur physically, a vapor‐infiltration method is utilized to achieve sulfur/carbon composite with covalent bonds, which can join electrochemical reaction without low voltage activation. A polydopamine derived N‐doped carbon layer is further coated on the composite to confine the high‐temperature‐induced gas‐phase sulfur inside the host. S and N dopants increase the polarity of the carbon host to restrict diffusion of sulfur, and its 3D porous structure provides a large storage area for sulfur. As a result, the obtained composite shows outstanding electrochemical performance with 467 mAh g?1 (1262 mAh g?1(sulfur)) at 0.1 A g?1, 270 mAh g?1 (730 mAh g?1(sulfur)) after 1000 cycles at 1 A g?1 and 201 mAh g?1 (543 mAh g?1(sulfur)) at 5.0 A g?1.  相似文献   

8.
Tailoring active sites in earth‐abundant non‐noble metal electrocatalysts are required toward widespread applications in sustainable energy fields. Herein, an integrated mesoporous heterostructure array is reported by a hydrogenation/nitridation‐induced in situ growth strategy. Highly conductive oxygen‐vacancies‐rich tungsten oxynitride (Vo‐WON) nanorod array acts as the backbone encapsulated by ultrathin nitrogen‐doped carbon (NC) nanolayers, forming high‐quality shell/core NC/Vo‐WON heterostructures. Density functional theory calculations reveal that defect‐rich heterostructure arrays not only enhance the conductivity and modulate electronic structure but also promote the adsorption and dissociation of reactants and offer substantial potential sites. As expected, porous NC/Vo‐WON array exhibits a small overpotential of 16 mV at the current density of 10 mA cm?2 and a low Tafel slope of 33 mV per decade in alkaline media, accompanied by negligible loss upon a large current density over 100 h. Benefiting from outstanding electrocatalytic hydrogen evolution reaction performance and stability, this defective heterostructure could serve as a prominent alternative electrocatalyst for renewable energy applications.  相似文献   

9.
The inhibitively high cost of the noble‐metal‐containing materials has become a major obstacle for the large‐scale application of rechargeable zinc‐air batteries (ZABs). To solve this problem in a practical way, a green and scalable method to prepare sandwich‐like reduced graphene oxide /carbon black/amorphous cobalt borate nanocomposites (rGO/CB/Co‐Bi) is reported. These composites are shown to be a highly efficient and robust bifunctional electrocatalyst for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In this system, the spontaneous assembly of the GO sheet and CB nanoparticles is demonstrated by noncovalent interactions to build the sandwich‐like structure with hierarchical pore distribution. The impressive ORR and OER activities of the obtained nanocomposite are attributed to the high conductivity, large surface area, and the hierarchically porous channels. With room‐temperature synthesis and significant activities shown in the demonstrative battery test, the prepared nanocomposite can potentially serve as an alternative for noble‐metal‐based rechargeable ZAB cathode materials.  相似文献   

10.
Rational construction of atomic‐scale interfaces in multiphase nanocomposites is an intriguing and challenging approach to developing advanced catalysts for both oxygen reduction (ORR) and evolution reactions (OER). Herein, a hybrid of interpenetrating metallic Co and spinel Co3O4 “Janus” nanoparticles stitched in porous graphitized shells (Co/Co3O4@PGS) is synthesized via ionic exchange and redox between Co2+ and 2D metal–organic‐framework nanosheets. This strategy is proven to effectively establish highways for the transfer of electrons and reactants within the hybrid through interfacial engineering. Specifically, the phase interpenetration of mixed Co species and encapsulating porous graphitized shells provides an optimal charge/mass transport environment. Furthermore, the defect‐rich interfaces act as atomic‐traps to achieve exceptional adsorption capability for oxygen reactants. Finally, robust coupling between Co and N through intimate covalent bonds prohibits the detachment of nanoparticles. As a result, Co/Co3O4@PGS outperforms state‐of‐the‐art noble‐metal catalysts with a positive half‐wave potential of 0.89 V for ORR and a low potential of 1.58 V at 10 mA cm?2 for OER. In a practical demonstration, ultrastable cyclability with a record lifetime of over 800 h at 10 mA cm?2 is achieved by Zn–air batteries with Co/Co3O4@PGS within the rechargeable air electrode.  相似文献   

11.
By employing in situ reduction of metal precursor and metal‐assisted carbon etching process, this study achieves a series of ultrafine transition metal‐based nanoparticles (Ni–Fe, Ni–Mo) embedded in N‐doped carbon, which are found efficient catalysts for electrolytic water splitting. The as‐prepared hybrid materials demonstrate outstanding catalytic activities as non‐noble metal electrodes rendered by the synergistic effect of bimetal elements and N‐dopants, the improved electrical conductivity, and hydrophilism. Ni/Mo2C@N‐doped porous carbon (NiMo‐polyvinylpyrrolidone (PVP)) and NiFe@N‐doped carbon (NiFe‐PVP) produce low overpotentials of 130 and 297 mV at a current density of 10 mA cm?2 as catalysts for hydrogen evolution reaction and oxygen evolution reaction, respectively. In addition, these binder‐free electrodes show long‐term stability. Overall water splitting is also demonstrated based on the couple of NiMo‐PVP||NiFe‐PVP catalyzer. This represents a simple and effective synthesis method toward a new type of nanometal–carbon hybrid electrodes.  相似文献   

12.
Searching for highly efficient and durable electrocatalysts for the hydrogen evolution reaction (HER) that function effectively at all pHs is of great interest to the scientific community, however it is still a grand challenge, because the HER kinetics of Pt in alkaline solutions are approximately two to three orders of magnitude lower than that in acidic solution. Herein, a new class of wrinkled, ultrathin Rh2P nanosheets for enhancing HER catalysis at all pHs is reported. They exhibit a small overpotential of 18.3 mV at 10 mA cm?2, low Tafel slope of 61.5 mV dec?1, and good durability in alkaline media, much better than the commercial Pt/C catalyst. Density functional theory calculations reveal that the active open‐shell effect from the P‐3p band not only promotes Rh‐4d for increased proton–electron charge exchange but also provides excellent p–p overlapping to locate the O‐related species as distributary center, which can benefit the HER process in alkaline media. It is also demonstrated that the present wrinkled, ultrathin Rh2P nanosheets are highly efficient and durable electrocatalysts toward HER in both acid and neutral electrolytes. The present work opens a new material design for ultrathin 2D metal phosphide nanostructures for the purpose of boosting HER performance at all pHs.  相似文献   

13.
In this work, a hierarchically porous and ultrathick “breathable” wood‐based cathode for high‐performance Li‐O2 batteries is developed. The 3D carbon matrix obtained from the carbonized and activated wood (denoted as CA‐wood) serves as a superconductive current collector and an ideal porous host for accommodating catalysts. The ruthenium (Ru) nanoparticles are uniformly anchored on the porous wall of the aligned microchannels (denoted as CA‐wood/Ru). The aligned open microchannels inside the carbon matrix contribute to unimpeded oxygen gas diffusion. Moreover, the hierarchical pores on the microchannel walls can be facilely impregnated by electrolyte, forming a continuous supply of electrolyte. As a result, numerous ideal triphase active sites are formed where electrolyte, oxygen, and catalyst accumulate on the porous walls of microchannels. Benefiting from the numerous well‐balanced triple‐phase active sites, the assembled Li‐O2 battery with the CA‐wood/Ru cathode (thickness: ≈700 µm) shows a high specific area capacity of 8.58 mA h cm?2 at 0.1 mA cm?2. Moreover, the areal capacity can be further increased to 56.0 mA h cm?2 by using an ultrathick CA‐wood/Ru cathode with a thickness of ≈3.4 mm. The facile ultrathick wood‐based cathodes can be applied to other cathodes to achieve a super high areal capacity without sacrificing the electrochemical performance.  相似文献   

14.
The role of vacancy defects is demonstrated to be positive in various energy‐related processes. However, introducing vacancy defects into single‐crystalline nanostructures with given facets and studying their defect effect on electrocatalytic properties remains a great challenge. Here this study deliberately introduces oxygen defects into single‐crystalline ultrathin Co3O4 nanosheets with O‐terminated {111} facets by mild solvothermal reduction using ethylene glycol under alkaline condition. As‐prepared defect‐rich Co3O4 nanosheets show a low overpotential of 220 mV with a small Tafel slope of 49.1 mV dec?1 for the oxygen evolution reaction (OER), which is among the best Co‐based OER catalysts to date and even more active than the state‐of‐the‐art IrO2 catalyst. Such vacancy defects are formed by balancing with reducing environments under solvothermal conditions, but are surprisingly stable even after 1000 cycles of scanning under OER working conditions. Density functional theory plus U calculation attributes the enhanced performance to the oxygen vacancies and consequently exposed second‐layered Co metal sites, which leads to the lowered OER activation energy of 2.26 eV and improved electrical conductivity. This mild solvothermal reduction concept opens a new door for the understanding and future designing of advanced defect‐based electrocatalysts.  相似文献   

15.
The increasing demand for portable and wearable electronics requires lightweight, thin, and highly flexible power sources, for example, flexible zinc‐air batteries (ZABs). The so‐far reported flexible ZAB devices mostly remain bulky, with a design consisting of two relatively thick substrates (e.g., carbon cloths and/or metal foams) and a gel electrolyte‐coated separator in between. Herein, an ultrathin (≈0.2 mm) solid‐state ZAB with high flexibility and performance is introduced by directly forming self‐standing active layers on each surface of an alkaline polymer membrane through an ink‐casting/hot‐pressing approach. A Fe/N‐doped 3D carbon with hierarchic pores and an interconnected network structure is used as cathode electrocatalyst, so that the backing gas‐diffusion layer (e.g., carbon cloth) can be abandoned. What is further, a microstructure‐modulating method to significantly increase the FeN4 active sites for oxygen reduction reaction is developed, thus significantly boosting the performance of the ZAB. The assembled solid‐state ZAB manifests remarkable peak power density of 250 mW cm?3 and high capacity of 150.4 mAh cm?3 at 8.3 mA cm?3, as well as excellent flexibility. The new design should provide valuable opportunity to the portable and wearable electronics.  相似文献   

16.
Various doped materials have been investigated to improve the structural stability of layered transition metal oxides for lithium‐ion batteries. Most doped materials are obtained through solid state methods, in which the doping of cations is not strictly site selective. This paper demonstrates, for the first time, an in situ electrochemical site‐selective doping process that selectively substitutes Li+ at Li sites in Mn‐rich layered oxides with Mg2+. Mg2+ cations are electrochemically intercalated into Li sites in delithiated Mn‐rich layered oxides, resulting in the formation of [Li1?xMgy][Mn1?zMz]O2 (M = Co and Ni). This Mg2+ intercalation is irreversible, leading to the favorable doping of Mg2+ at the Li sites. More interestingly, the amount of intercalated Mg2+ dopants increases with the increasing amount of Mn in Li1?x[Mn1?zMz]O2, which is attributed to the fact that the Mn‐to‐O electron transfer enhances the attractive interaction between Mg2+ dopants and electronegative Oδ? atoms. Moreover, Mg2+ at the Li sites in layered oxides suppresses cation mixing during cycling, resulting in markedly improved capacity retention over 200 cycles. The first‐principle calculations further clarify the role of Mg2+ in reduced cation mixing during cycling. The new concept of in situ electrochemical doping provides a new avenue for the development of various selectively doped materials.  相似文献   

17.
The most efficient electrocatalyst for the hydrogen evolution reaction (HER) is a Pt‐based catalyst, but its high cost and nonperfect efficiency hinder wide‐ranging industrial/technological applications. Here, an electrocatalyst of both ruthenium (Ru) single atoms (SAs) and N‐doped‐graphitic(GN)‐shell‐covered nitrided‐Ru nanoparticles (NPs) (having a Ru‐Nx shell) embedded on melamine‐derived GN matrix { 1 : [Ru(SA)+Ru(NP)@RuNx@GN]/GN}, which exhibits superior HER activity in both acidic and basic media, is presented. In 0.5 m H2SO4/1 m KOH solutions, 1 shows diminutive “negative overpotentials” (?η = |η| = 10/7 mV at 10 mA cm?2, lowest ever) and high exchange current densities (4.70/1.96 mA cm?2). The remarkable HER performance is attributed to the near‐zero free energies for hydrogen adsorption/desorption on Ru(SAs) and the increased conductivity of melamine‐derived GN sheets by the presence of nitrided‐Ru(NPs). The nitridation process forming nitrided‐Ru(NPs), which are imperfectly covered by a GN shell, allows superb long‐term operation durability. The catalyst splits water into molecular oxygen and hydrogen at 1.50/1.40 V (in 0.1 m HClO4/1 m KOH), demonstrating its potential as a ready‐to‐use, highly effective energy device for industrial applications.  相似文献   

18.
3,4‐Dihydroxy‐2‐butanone‐4‐phosphate synthase (DHBPS) encoded by ribB gene is one of the first enzymes in riboflavin biosynthesis pathway and catalyzes the conversion of ribulose‐5‐phosphate (Ru5P) to 3,4‐dihydroxy‐2‐butanone‐4‐phosphate and formate. DHBPS is an attractive target for developing anti‐bacterial drugs as this enzyme is essential for pathogens, but absent in humans. The recombinant DHBPS enzyme of Salmonella requires magnesium ion for its activity and catalyzes the formation of 3,4‐dihydroxy‐2‐butanone‐4‐phosphate from Ru5P at a rate of 199 nmol min?1 mg?1 with Km value of 116 μM at 37°C. Further, we have determined the crystal structures of Salmonella DHBPS in complex with sulfate, Ru5P and sulfate‐zinc ion at a resolution of 2.80, 2.52, and 1.86 Å, respectively. Analysis of these crystal structures reveals that the acidic loop (residues 34–39) responsible for the acid‐base catalysis is disordered in the absence of substrate or metal ion at the active site. Upon binding either substrate or sulfate and metal ions, the acidic loop becomes stabilized, adopts a closed conformation and interacts with the substrate. Our structure for the first time reveals that binding of substrate Ru5P alone is sufficient for the stabilization of the acidic active site loop into a closed conformation. In addition, the Glu38 residue from the acidic active site loop undergoes a conformational change upon Ru5P binding, which helps in positioning the second metal ion that stabilizes the Ru5P and the reaction intermediates. This is the first structural report of DHBPS in complex with either substrate or metal ion from any eubacteria. Proteins 2010. © 2010 Wiley‐Liss, Inc.  相似文献   

19.
Lithium metal is the most promising anode material for high‐energy‐density batteries due to its high specific capacity of 3860 mAh g?1 and low reduction potential of ?3.04 V versus standard hydrogen electrode. However, huge volume change, safety concerns, and low efficiency impede the practical applications of Li metal anodes. Herein, it is shown that the nitrogen‐doped graphene modified 3D porous Cu (3DCu@NG) current collector can mitigate the above problems. The N‐doped graphene, coating on the surface of 3D current collector, not only contributes to a uniform Li+ flux, but also leads to a scattered distribution of electrons throughout the surface, finally contributing to a uniform Li deposition and the improved electrochemical performance. In addition, the continuously porous structure of 3DCu@NG provides a space for the metallic Li deposition and could effectually accommodate the volume expansion during cycling. As a result, the Li‐3DCu@NG anode exhibits a high areal capacity of 4 mAh cm?2, a high Li utilization of ≈98%, and an ultralow voltage hysteresis of ≈19 mV. The multifunctional N‐doped graphene modified 3D porous current collector promisingly provides a strategy for safe and high‐energy lithium metal anodes.  相似文献   

20.
Metal‐organic coordination frameworks have been widely used as efficient precursors for the preparation of functional carbon‐based materials with various nanostructures. However, to date, the design of 2D carbon nanostructures from single coordination frameworks remains a great challenge. Herein, an efficient strategy for the fabrication of N‐rich porous carbon nanosheets from 2D Zn‐hexamine coordination framework nanosheets is developed. Remarkably, the N‐doping level of carbon nanosheets can attain 16.54 at%. In addition, the thickness of the carbon nanosheets can effectively be tuned by simply adjusting the molar ratio of the starting materials. As a proof‐of‐concept application, the as‐prepared carbon nanosheets as an anode material for sodium‐ion batteries exhibit an ultrafast sodium storage capability of 194 mAh g?1 even at 10 A g?1. As far as it is known, such a high‐rate capability has been rarely achieved in previous studies on carbonaceous anode materials for Na‐ion storage. Moreover, this approach is readily controllable and could be extended to prepare a series of 2D N‐doped carbon‐based nanomaterials on a large scale.  相似文献   

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