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1.
《中国化学快报》2020,31(10):2641-2644
The high cost and low reserves of noble metals greatly hinder their practical applications in new energy production and conversion. The exploration of cost-effective alternative electrocatalysts with the ability to drive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is extremely significant to promote overall water splitting. Herein, ultrathin CoSe2/CNTs nanocomposites have been synthesized by a facile two-step method, where the ultrathin Co-MOF (metal organic-framework) decorated with cable-like carbon nanotubes (CNTs) (Co-MOF/CNTs) was initially fabricated, and followed a low-temperature selenization process. The ultrathin CoSe2 nanosheets as well as the superior conductivity of CNTs synergistically resulted in abundant active sites and enhanced conductivity to boost the electrocatalytic activity. The as-prepared CoSe2/CNTs electrocatalysts exhibited an overpotential of 190 mV and 300 mV vs. reversible hydrogen electrode (RHE) at a current density of 10 mA/cm2 for the HER and OER in alkaline solution, respectively, and demonstrated superior durability. Furthermore, the as-prepared bifunctional CoSe2/CNTs electrocatalysts can act as cathode and anode in an electrolyzer, showing a cell voltage of 1.75 V at 10 mA/cm2 for overall water splitting.  相似文献   

2.
The development of active,low-cost and durable bifunctional electrocatalysts toward both oxygen evolution reaction(OER) and hydro gen evolution react ion(HER) a re important for overall water splitting.Here,well-defined arrays of vanadium-iron bimetal organic frameworks(VFe-MOF) with controllable stoichiometry have been successfully prepared on nickel foam(NF).The as-fabricated VFe-MOF@NF electrode exhibits excellent electrocatalytic activity and durability for OER and HER in alkaline medium.The material's overpotentials of 10 mA/cm~2 are 246 mV for OER and 147 mV for HER,respectively.The electrolyzer made from the VFe-MOF@NF electrodes as both the cathode and anode in 1 mol/L KOH needs only a voltage of 1.61 V to reach a current density of 10 mA/cm~2.The superior performance of VFeMOF@NF can be attributed to the morphological control and electronic regulation of the bimetals,that is,1) the exposure of the active sites at electrocatalyst/electrolyte interfaces due to the array structure;2)the synergistic effect of vanadium and iron metals on electro-catalyzing the overall water splitting.  相似文献   

3.
The development of low-cost and highly efficient bifunctional electrocatalysts toward oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) is of critical importance for clean energy devices such as fuel cells and metal-air batteries.Herein,a sophisticated na nostructure composed of CoS,Co and MoC nanoparticles incorporated in N and S dual-doped porous carbon nanofibers(CoS/Co/MoC-N,SPCNFs) as a high-efficiency bifunctional electrocatalyst is designed and synthesized via an efficient multistep strategy.The as-prepared CoS/Co/MoC-N,S-PCNFs exhibit a positive half-wave potential(E_(1/2)) of0.871 V for ORR and a low overpotential of 289 mV at 10 mA/cm~2 for OER,outperforming the non-noble metal-based catalysts reported.Furthermore,the assembled Zn-air battery based on CoS/Co/MoC-N,SPCNFs delivers an excellent power density(169.1 mW/cm~2),a large specific capacity(819.3 mAh/g) and robust durability,demonstrating the great potential of the as-developed bifunctional electrocatalyst in practical applications.This work is expected to inspire the design of advanced bifunctional nonprecious metal-based electrocatalysts for energy storage.  相似文献   

4.
In order to realize industrial production of hydrogen through water splitting,it is essential to develop a cost-efficient and scalable approach to synthesize nonprecious electrocatalysts with sufficiently high activity and stability to replace commercial noble-metal-based electrocatalysts.Herein we synthesize cobalt phosphide nanoparticles dispersed within nitrogen-doped carbon nanotube network(CP@NCNT) via scalable spray drying and thermal treatments.As a multifunctional electrocatalyst,the CP@NCNT hybrid delivers outstanding activity for HER(in both acidic and alkaline electrolytes),OER and overall water splitting.Remarkably,it shows an ultra-low overpotental of 94 mV to obtain 10 mA cm-2 in HER.It also demonstrates outstanding activity in overall water splitting,requiring only 1.619 V to deliver 10 mA cm-2with more than 72 h’ long-term stability.The combination of notable performance,multi-functionality and highly scalable spray-drying synthesis method enables this material as a novel and cost-efficient transition metal-based electrocatalysts for overall water splitting.  相似文献   

5.
《Journal of Energy Chemistry》2017,26(6):1196-1202
The large-scale synthesis of efficient nonprecious bifunctional electrocatalysts for overall water splitting is a great challenge for future renewable energy conversion systems. Herein, Ni_2P nanosheet arrays directly grown on three-dimensional(3 D) Ni foam(Ni P/NF) are fabricated by hydrothermal treatment of metallic Ni foam with H_2O_2 solution and subsequent phosphidation with NaH_2PO_2. The Ni P/NF as electrocatalyst exhibits superior activities for both hydrogen evolution reaction(HER) and oxygen evolution reaction(OER). Most importantly, employing both as the cathode and anode for an alkaline water electrolyzer, Ni P/NF only requires a cell voltage of 1.63 V to reach a current density of 10 mV cm~(-2), together with stronger durability. Preliminary catalytic information suggests that the tailored 3 D superstructure and integrated electrode configurations afford improved active sties and enhanced electron/mass transfer,responding for the outstanding activity and stability.  相似文献   

6.
为简化电解水催化剂的合成过程和优化电解水操作系统, 双功能电解水催化剂的研究, 特别是在碱性条件下同时具有优异催化氢析出和氧析出反应性能的双功能电催化剂的研究尤为重要. 其中, 过渡金属硫化物, 特别是 CoNi 硫化物, 被报道有与氢化酶类似的催化活性中心, 从而具有优异的催化氢析出和催化氧析出反应性能. 虽然有关对过渡金属硫化物的研究很多, 但主要集中在具有一维纳米线和二维纳米片形貌结构的过渡金属硫化物. 不幸的是, 这些形貌结构的过渡金属硫化物在电催化过程中容易聚集和受限于电荷传输能力. 三维纳米结构的材料具有较大的比表面积以分布更多的活性位点和拥有良好的电子传输能力, 所以, 开发三维纳米结构的过渡金属硫化物材料可能是改进其催化电解水性能的一个好途径. 本文采用简单的两步水热法, 通过硫化合成的 CoNi 前体得到了长于泡沫镍上的三维百合花状的 CoNi2S4(Co-Ni2S4/Ni). 它只需要 54 mV 的过电位即可获得 10 mA cm-2的催化氢析出反应电流, 是最好的碱性催化氢析出反应电极材料之一. 它在驱动 100 mA cm-2的催化氧析出反应电流时也只需要 328 mV 的过电位. 另外, 把 CoNi2S4/Ni 分别作为阴极和阳极组装成双电极碱性水电解槽时, 它只需要 1.56 V 的电压即可获取 10 mA cm-2的催化全电解水电流并具有良好的催化全电解水稳定性.扫描电子显微镜、透射电子显微镜和 N2吸脱附曲线测试结果表明, 该三维百合花状的 CoNi2S4/Ni 的表面粗糙度高和拥有多孔特性. 多孔结构的 CoNi2S4/Ni 可提供更多可接触的催化活性位点, 也有利于催化过程中的电解质和生成的气体的扩散与传递. 交流阻抗图谱测试结果表明, CoNi2S4/Ni 具有良好的电子传输能力. 另外, 不同于前期对尖晶石结构的硫化物 AB2S4的研究结果, XPS 结果表明, CoNi2S4/Ni 中含有 Niб+和 Sб-活性物种, 表明 CoNi2S4具有与活性氢化酶类似的活 性中心. Niδ+和 Sδ-可分别作为氢氧根和质子的接收体, 协助促进吸附的水分子的分离, 从而提高材料的催化性能. 所以, Niδ+和 Sδ-活性物种的出现, 大比表面积的三维百合花状多孔结构和良好的电荷传输能力等特性集合于 CoNi2S4/Ni 上使得CoNi2S4/Ni 具有优异的催化氢析出和催化氧析出反应性能.  相似文献   

7.
《印度化学会志》2022,99(11):100775
A bifunctional electrocatalyst interface requires a superior charge transfer and good electric conductivity to produce an efficient and stable water splitting reaction. In the context of controlling the electrochemical activity of bifunctional catalytic materials, we demonstrate a novel approach to bridge conductive C-Qd-Mn interfaces with precise control. The excellent performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can be dominantly attributed to the unique structure of C-Qds-Mn, which provides abundant active sites and facilitates electron transfer between electrode and electrolyte. Eco-friendly C-Qds were synthesized using a large-scale thermal assisted technique and utilized as electrocatalysts with Mn3O4 in alkaline splitting ToF (Turn over Frequency) calculation to make an effective combination. Due to their increased ECSA, conductivity, and electron-hole transfer, the prepared C-Qds-Mn delivered excellent HER/OER (0.494 V/1.6671V) activity, lower Standard deviation 0.006 V and 0.009V, surpassing the 10 mA limit comparable to commercially.  相似文献   

8.
Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π‐electron‐assisted strategy to anchor single‐atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four‐fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water‐splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm?2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC3 sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.  相似文献   

9.
Both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are crucial to water splitting, but require alternative active sites. Now, a general π‐electron‐assisted strategy to anchor single‐atom sites (M=Ir, Pt, Ru, Pd, Fe, Ni) on a heterogeneous support is reported. The M atoms can simultaneously anchor on two distinct domains of the hybrid support, four‐fold N/C atoms (M@NC), and centers of Co octahedra (M@Co), which are expected to serve as bifunctional electrocatalysts towards the HER and the OER. The Ir catalyst exhibits the best water‐splitting performance, showing a low applied potential of 1.603 V to achieve 10 mA cm?2 in 1.0 m KOH solution with cycling over 5 h. DFT calculations indicate that the Ir@Co (Ir) sites can accelerate the OER, while the Ir@NC3 sites are responsible for the enhanced HER, clarifying the unprecedented performance of this bifunctional catalyst towards full water splitting.  相似文献   

10.
One of the challenges to realize large‐scale water splitting is the lack of active and low‐cost electrocatalysts for its two half reactions: H2 and O2 evolution reactions (HER and OER). Herein, we report that cobalt‐phosphorous‐derived films (Co‐P) can act as bifunctional catalysts for overall water splitting. The as‐prepared Co‐P films exhibited remarkable catalytic performance for both HER and OER in alkaline media, with a current density of 10 mA cm?2 at overpotentials of ?94 mV for HER and 345 mV for OER and Tafel slopes of 42 and 47 mV/dec, respectively. They can be employed as catalysts on both anode and cathode for overall water splitting with 100 % Faradaic efficiency, rivalling the integrated performance of Pt and IrO2. The major composition of the as‐prepared and post‐HER films are metallic cobalt and cobalt phosphide, which partially evolved to cobalt oxide during OER.  相似文献   

11.
Oxygen evolution reaction(OER) is a key process for electrochemical water splitting due to its intrinsic large overpotential. Recently, layered double hydroxides(LDHs), especially Ni Fe-LDH, have been regarded as highly performed electrocatalysts for OER in alkaline condition. Here we first present a new class of Ni La-LDH electrocatalyst synthesized by an electrochemical process for efficient water splitting. The as-prepared NiL a-LDH nanosheet arrays(NSAs) give remarkable electrochemical activity and durability under alkaline environments, with a low overpotential of 209 mV for OER to deliver a current density of 10 mA cm~(-2), surpassing most of previous reported LDHs eletrocatalysts. The presence of NiLa-LDH in this work extends the studies about LDHs-based electrocatalysts, which will benefit the development of electrochemical energy storage and conversion systems.  相似文献   

12.
Developing highly active, stable and robust electrocatalysts based on earth‐abundant elements for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is important for many renewable energy conversion processes. Herein, NixCo3‐xO4 nanoneedle arrays grown on 3D porous nickel foam (NF) was synthesized as a bifunctional electrocatalyst with OER and HER activity for full water splitting. Benefiting from the advantageous structure, the composite exhibits superior OER activity with an overpotential of 320 mV achieving the current density of 10 mA cm?2. An exceptional HER activity is also acquired with an overpotential of 170 mV at the current density of 10 mA cm?2. Furthermore, the catalyst also shows the superior activity and stability for 20 h when used in the overall water splitting cell. Thus, the hierarchical 3D structure composed of the 1D nanoneedle structure in NixCo3‐xO4/NF represents an avenue to design and develop highly active and bifunctional electrocatalysts for promising energy conversion.  相似文献   

13.
析氧反应(OER)在能量转换和储存技术中扮演着重要角色,例如在水分解和金属空气电池中,电催化剂的发展是主要任务.本文采用钴基的类沸石咪唑酯骨架结构材料(ZIFs)作为前驱体,在氩气保护气氛下,成功制备了氮掺杂钴镍磷多孔碳多面体电催化剂(CoNiP/NC).首先,采用ZIF-67作为前驱体,将ZIF-67和六水合硝酸镍按照一定比例在乙醇溶液中搅拌30 min,达到掺杂镍的目的,然后将其在不同温度下煅烧,得到的样品在300 oC氩气保护气氛下磷化,得到最终产物.所有电催化剂均通过控制碳化和磷化作用温度获得.通过对样品ZIF-67Ni进行EDS分析,证明镍成功负载到ZIF-67上,XPS结果也证明了这一点.由扫描电镜图可以看出,前驱体ZIF-67在负载Ni之后,样品表面形貌发生明显变化,表面变得粗糙,有明显的条文.磷化后样品的XRD结果说明磷化方法是成功的,同时XPS结果表明样品中有P元素存在.从扫描电镜图片可以明显看出,样品在煅烧之后表面形貌发生明显变化,由棱角明显变为表面粗糙,但是并未发生明显的团聚现象.XPS显示,样品CoNiP/NC700(700指煅烧温度(oC))中存在钴、镍、磷、碳、氮、氧这六种元素,另外还分析了其高分辨图.结果显示,电催化剂CoNiP/NC700表现出优越的电催化效率,在碱性溶液的电流密度10 mA/cm~2条件下,其开路电压约为220 mV,过电位约为300 mV.掺杂镍之后的样品性能比煅烧ZIF-67的样品好,说明镍对于提高析氧反应效率有益;同样,磷化之后样品的OER性能也有所提高.相比较而言,对于磷化之后的样品,煅烧温度是700℃时,OER催化效率最好.磷化杂化材料优越的电催化活性是由于其强的电子耦合相互作用而产生的协同效应,在镍、磷、碳等方面具有较强的协同效应.相互联系的非定形碳不仅固定了活性碳化合物以避免聚集,而且还为电子转移提供了传导通道.对样品CoNiP/NC700进行了稳定性测试,结果表明其稳定性较好,在循环10 h之后,活性仅下降了4%.这一研究表明,该复合电催化剂可能是电催化氧化反应的一个很有前景的候选催化剂.  相似文献   

14.
Transitional metal alloy and compounds have been developed as the low cost and efficient bifunctional electrocatalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).However,a high mass loading of these catalysts is commonly needed to achieve acceptable catalytic performance,which could cause such problems as battery weight gain,mass transport blocking,and catalyst loss.We report herein the preparation of fine CoNi nanoparticles(5-6 nm)anchored inside a nitrogendoped defective carbon nanotube network(CoNi@N-DCNT)by a transient Joule heating method.When utilized as an electrocatalyst for oxygen reduction and evolution in alkaline media,the CoNi@N-DCNT film catalyst with a very low mass loading of 0.06 mg cm-2 showed excellent bifunctional catalytic performance.For ORR,the onset potential(Eonset)and the half-wave potential(E1/2)were 0.92 V versus reversible hydrogen electrode(vs.RHE)and 0.83 V(vs.RHE),respectively.For OER,the potential at the current density(J)of 10 mA cm-2(E10)was 1.53 V,resulting in an overpotential of 300 mV much lower than that of the commercial RuO2 catalyst(320 mV).The potential gap between E1/2 and E10 was as small as 0.7 V.Considering the low mass loading,the mass activity at E10 reached at 123.2 A g-1,much larger than that of the RuO2 catalyst and literature results of transitional metal-based bifunctional catalysts.Moreover,the CoNi@N-DCNT film catalyst showed very good long-term stability during the ORR and OER test.The excellent bifunctional catalytic performance could be attributed to the synergistic effect of the bimetal alloy.  相似文献   

15.
《中国化学快报》2023,34(7):107812
Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction (OER) and the hydrogen evolution reduction (HER) in the overall water splitting (OWS) for the sustainable production of clean fuels. Herein, comprehensive density functional theory (DFT) computations were performed to explore the potential of several single transition metal (TM) atoms anchored on various S-doped black phosphorenes (TM/Snx-BP) for bifunctional OWS electrocatalysis. The results revealed that these candidates display good stability, excellent electrical conductivity, and diverse spin moments. Furthermore, the Rh/S12-BP catalyst was identified as an eligible bifunctional catalyst for OWS process due to the low overpotentials for OER (0.43 V) and HER (0.02 V), in which Rh and its adjacent P atoms were identified as the active sites. Based on the computed Gibbs free energies of OH*, O*, OOH* and H*, the corresponding volcano plots for OER and HER were established. Interestingly, the spin moments and the charge distribution of the active sites determine the catalytic trends of OER and HER. Our findings not only propose a promising bifunctional catalyst for OWS, but also widen the potential application of BP in electrocatalysis.  相似文献   

16.
The development of high-efficiency bifunctional electrocatalysts toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline surroundings is essential and challenging for the large-scale generation of clean hydrogen. Herein, a novel self-assembled two-dimensional (2 D) NiO/CeO2 heterostructure (HS) consisting of NiO and CeO2 nanocrystals is prepared through a facile two-step approach, and utilized as an enhanced bifunctional electrocatalyst for the HER and OER under alkaline conditions. It is concluded that this 2 D NiO/CeO2 HS, rich in oxygen vacancies, demonstrates attractive electrocatalytic properties for both the HER and OER in 1 m KOH, including low onset overpotential (η1), η10 and Tafel slope, excellent durability, as well as large active surface area. Therefore, the self-assembled 2 D NiO/CeO2 HS is believed to be an efficient bifunctional electrocatalyst toward the HER and OER.  相似文献   

17.
Electrocatalytic water splitting into H2 and O2 is a key technology for carbon‐neutral energy. Here, we report a modular materials design leading to noble metal‐free composite electrocatalysts, which combine high electrical conductivity, high OER and HER reactivity and high durability. The scalable bottom‐up fabrication allows the stable deposition of mixed metal oxide nanostructures with different functionalities on copper foam electrodes. The composite catalyst shows sustained OER and HER activity in 0.1 m aqueous KOH over prolonged periods (t>10 h) at low overpotentials (OER: ≈300 mV; HER: ≈100 mV) and high faradaic efficiencies (OER: ≈100 %, HER: ≈98 %). The new synthetic concept will enable the development of multifunctional, mixed metal oxide composites as high‐performance electrocatalysts for challenging energy conversion and storage reactions.  相似文献   

18.
《中国化学快报》2021,32(8):2484-2488
Electrochemical water splitting is a facile and effective route to generate pure hydrogen and oxygen.However,the sluggish kinetics of hydrogen evolution reaction(HER) and especially oxygen evolution reaction(OER) hinder the water splitting efficiency.Meanwhile,the high-cost of noble-metal catalysts limit their actual application.It is thus highly urgent to exploit an economical and earthabundant bifunctional HER and OER electrocatalyst to simplify procedure and reduce cost.Herein,we synthesize the three-dimensionally ordered macro-/mesoporous(3 DOM/m) Ni_xCo_(100-x) alloys with distinctive structure and large surface area via a dual-templating technique.Among them,the3 DOM/m Ni_(61)Co_(39) shows the lowest overpotentials of 121 mV and 241 mV at 10 mA/cm~2 for HER and OER,respectively.Furthermore,when employed for water splitting,the Ni_(61)Co_(39) only requires 1.60 V to approach 10 mA/cm2 and presents excellent stability.These encouraging performances of the Ni_(61)Co_(39)render it a promising bifunctional catalyst for overall water splitting.  相似文献   

19.
The development of transition‐metal‐oxides (TMOs)‐based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter‐doped ruthenium–cobalt oxide [(Ru–Co)Ox] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)Ox nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm?2 and a small Tafel slope of 23.5 mV dec?1, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm?2. As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm?2 for alkaline overall water splitting.  相似文献   

20.
The development of transition-metal-oxides (TMOs)-based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter-doped ruthenium–cobalt oxide [(Ru–Co)Ox] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)Ox nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm−2 and a small Tafel slope of 23.5 mV dec−1, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm−2. As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm−2 for alkaline overall water splitting.  相似文献   

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