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1.
The electrocatalytic CO2 reduction reaction (CO2RR) is an attractive technology for CO2 valorization and high-density electrical energy storage. Achieving a high selectivity to C2+ products, especially ethylene, during CO2RR at high current densities (>500 mA cm−2) is a prized goal of current research, though remains technically very challenging. Herein, it is demonstrated that the surface and interfacial structures of Cu catalysts, and the solid–gas–liquid interfaces on gas-diffusion electrode (GDE) in CO2 reduction flow cells can be modulated to allow efficient CO2RR to C2+ products. This approach uses the in situ electrochemical reduction of a CuO nanosheet/graphene oxide dots (CuO C(O)) hybrid. Owing to abundant Cu O C interfaces in the CuO C(O) hybrid, the CuO nanosheets are topologically and selectively transformed into metallic Cu nanosheets exposing Cu(100) facets, Cu(110) facets, Cu[n(100) × (110)] step sites, and Cu+/Cu0 interfaces during the electroreduction step,  the faradaic efficiencie (FE) to C2+ hydrocarbons was reached as high as 77.4% (FEethylene ≈ 60%) at 500 mA cm−2 . In situ infrared spectroscopy and DFT simulations demonstrate that abundant Cu+ species and Cu0/Cu+ interfaces in the reduced CuO C(O) catalyst improve the adsorption and surface coverage of *CO on the Cu catalyst, thus facilitating C C coupling reactions.  相似文献   

2.
Electrochemical reduction of carbon dioxide (CO2RR) product distribution has been identified to be dependent on various surface factors, including the Cu facet, morphology, chemical states, doping, etc., which can alter the binding strength of key intermediates such as *CO and *OCCO during reduction. Therefore, in-depth knowledge of the Cu catalyst surface and identification of the active species under reaction conditions aid in designing efficient Cu-based electrocatalysts. This progress report categorizes various Cu-based electrocatalysts into four main groups, namely metallic Cu, Cu alloys, Cu compounds (Cu + non-metal), and supported Cu-based catalysts (Cu supported by carbon, metal oxides, or polymers). The detailed mechanisms for the selective CO2RR are presented, followed by recent relevant developments on the synthetic procedures for preparing Cu and Cu-based nanoparticles. Herein, the potential link between the Cu surface and CO2RR performance is highlighted, especially in terms of the chemical states, but other significant factors such as defective sites and roughened morphology of catalysts are equally considered during the discussion of current studies of CO2RR with Cu-based electrocatalysts to fully understand the origin of the significant enhancement toward C2 formation. This report concludes by providing suggestions for future designs of highly selective and stable Cu-based electrocatalysts for CO2RR.  相似文献   

3.
Limited comprehension of the reaction mechanism has hindered the development of catalysts for CO2 reduction reactions (CO2RR). Here, the bimetallic AgCu nanocatalyst platform is employed to understand the effect of the electronic structure of catalysts on the selectivity and activity for CO2 electroreduction to CO. The atomic arrangement and electronic state structure vary with the atomic ratio of Ag and Cu, enabling tunable d-band centers to optimize the binding strength of key intermediates. Density functional theory calculations confirm that the variation of Cu content greatly affects the free energy of *COOH, *CO (intermediate of CO), and *H (intermediates of H2), which leads to the change of the rate-determining step. Specifically, Ag96Cu4 reduces the free energy of the formation of *COOH while maintaining a relatively high theoretical overpotential for hydrogen evolution reaction(HER), thus achieving the best CO selectivity. While Ag70Cu30 shows relatively low formation energy of both *COOH and *H, the compromised thermodynamic barrier and product selectivity allows Ag70Cu30 the best CO partial current density. This study realizes the regulation of the selectivity and activity of electrocatalytic CO2 to CO, which provides a promising way to improve the intrinsic performance of CO2RR on bimetallic AgCu.  相似文献   

4.
Electrochemical CO2 reduction reaction (CO2RR) is an effective approach to address CO2 emission, promote recycling, and synthesize high-value multi-carbon (C2+) chemicals for storing renewable electricity in the long-term. The construction of multilayer-bound nanoreactors to achieve management of intermediate CO is a promising strategy for tandem to C2+ products. In this study, a series of Ag@Cu2O nanoreactors consisting of an Ag-yolk and a multilayer confined Cu shell is designed to profile electrocatalytic CO2RR reactions. The optimized Ag@Cu2O-2 nanoreactor exhibits a 74% Faradaic efficiency during the C2+ pathway and remains stable for over 10 h at a bias current density of 100 mA cm−2. Using the finite element method, this model determines that the certain volume of cavity in the Ag@Cu2O nanoreactors facilitates on-site CO retention and that multilayers of Cu species favor CO capture. Density functional theory calculations illustrate that the biased generation of ethanol products may arise from the (100)/(111) interface of the Cu layer. In-depth explorations in multilayer-bound nanoreactors provide structural and interfacial guidance for sequential coupling of CO2RR intermediates for efficient C2+ generation.  相似文献   

5.
Molecular catalysts have been receiving increasingly attention in the electrochemical CO2 reduction reaction (CO2RR) with attractive features such as precise catalytic sites and tunable ligands. However, the insufficient activity and low selectivity of deep reduction products restrain the utilization of molecular catalysts in CO2RR. Herein, a donor–acceptor modified Cu porphyrin (CuTAPP) is developed, in which amino groups are linked to donate electrons toward the central CuN4 site to enhance the CO2RR activity. The CuTAPP catalyst exhibited an excellent CO2-to-CH4 electroreduction performance, including a high CH4 partial current density of 290.5 mA cm−2 and a corresponding Faradaic efficiency of 54.8% at –1.63 V versus reversible hydrogen electrode in flow cells. Density functional theory calculations indicated that CuTAPP presented a much lower energy gap in the pathway of producing *CHO than Cu porphyrin without amino group modification. This work suggests a useful strategy of introducing designed donor–acceptor structures into molecular catalysts for enhancing electrochemical CO2 conversion toward deep reduction products.  相似文献   

6.
Single‐atom Co catalyst Co‐Tpy‐C with well‐defined sites is synthesized by pyrolysis of a Co terpyridine (Tpy) organometallic complex. The Co‐Tpy‐C catalyst exhibits excellent activity for the electrochemical CO2 reduction reaction in aqueous electrolyte, with CO faradaic efficiency (FE) of over 95% from ?0.7 to ?1.0 V (vs RHE). By comparison, catalysts without Co or Tpy ligand added do not show any high CO FE. When simulated flue gas with 15% of CO2 is used as the source of CO2, CO FE is kept at 90.1% at ?0.5 V versus RHE. During gas phase flow electrolysis using simulated flue gas, the CO partial current density is further increased to 86.4 mA cm?2 and CO FE reached >90% at the cell voltage of 3.4 V. Experiments and density functional theory calculations indicate that uniform single‐atom Co–N4 sites mainly contribute to the high activity for CO2 reduction.  相似文献   

7.
Electrochemical conversion of carbon dioxide (electrochemical reduction of carbon dioxide) to value‐added products is a promising way to solve CO2 emission problems. This paper describes a facile one‐pot approach to synthesize palladium–copper (Pd–Cu) bimetallic catalysts with different structures. Highly efficient performance and tunable product distributions are achieved due to a coordinative function of both enriched low‐coordinated sites and composition effects. The concave rhombic dodecahedral Cu3Pd (CRD‐Cu3Pd) decreases the onset potential for methane (CH4) by 200 mV and shows a sevenfold CH4 current density at ?1.2 V (vs reversible hydrogen electrode) compared to Cu foil. The flower‐like Pd3Cu (FL‐Pd3Cu) exhibits high faradaic efficiency toward CO in a wide potential range from ?0.7 to ?1.3 V, and reaches a fourfold CO current density at ?1.3 V compared to commercial Pd black. Tafel plots and density functional theory calculations suggest that both the introduction of high‐index facets and alloying contribute to the enhanced CH4 current of CRD‐Cu3Pd, while the alloy effect is responsible for high CO selectivity of FL‐Pd3Cu.  相似文献   

8.
Zhu  Yating  Cui  Xiaoya  Liu  Huiling  Guo  Zhenguo  Dang  Yanfeng  Fan  Zhanxi  Zhang  Zhicheng  Hu  Wenping 《Nano Research》2021,14(12):4471-4486

Electrochemical CO2 reduction reaction (CO2RR) is an attractive pathway for closing the anthropogenic carbon cycle and storing intermittent renewable energy by converting CO2 to valuable chemicals and fuels. The production of highly reduced carbon compounds beyond CO and formate, such as hydrocarbon and oxygenate products with higher energy density, is particularly desirable for practical applications. However, the productivity towards highly reduced chemicals is typically limited by high overpotential and poor selectivity due to the multiple electron-proton transfer steps. Tandem catalysis, which is extensively utilized by nature for producing biological macromolecules with multiple enzymes via coupled reaction steps, represents a promising strategy for enhancing the CO2RR performance. Improving the efficiency of CO2RR via tandem catalysis has recently emerged as an exciting research frontier and achieved significant advances. Here we describe the general principles and also considerations for designing tandem catalysis for CO2RR. Recent advances in constructing tandem catalysts, mainly including bimetallic alloy nanostructures, bimetallic heterostructures, bimetallic core-shell nanostructures, bimetallic mixture catalysts, metal-metal organic framework (MOF) and metal-metallic complexes, metal-nonmetal hybrid nanomaterials and copper-free hybrid nanomaterials for boosting the CO2RR performance are systematically summarized. The study of tandem catalysis for CO2RR is still at the early stage, and future research challenges and opportunities are also discussed.

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9.
Electrochemical CO2 reduction reaction (CO2RR) to value-added chemicals/fuels is an effective strategy to achieve the carbon neutral. Palladium is the only metal to selectively produce formate via CO2RR at near-zero potentials. To reduce cost and improve activity, the high-dispersive Pd nanoparticles on hierarchical N-doped carbon nanocages (Pd/hNCNCs) are constructed by regulating pH in microwave-assisted ethylene glycol reduction. The optimal catalyst exhibits high formate Faradaic efficiency of >95% within −0.05–0.30 V and delivers an ultrahigh formate partial current density of 10.3 mA cm−2 at the low potential of −0.25 V. The high performance of Pd/hNCNCs is attributed to the small size of uniform Pd nanoparticles, the optimized intermediates adsorption/desorption on modified Pd by N-doped support, and the promoted mass/charge transfer kinetics arising from the hierarchical structure of hNCNCs. This study sheds light on the rational design of high-efficient electrocatalysts for advanced energy conversion.  相似文献   

10.
Ni single-atom catalysts (SACs) are appealing for electrochemical reduction CO2 reduction (CO2RR). However, regulating the balance between the activity and conductivity remains a challenge to Ni SACs due to the limitation of substrates structure. Herein, the intrinsic performance enhancement of Ni SACs anchored on quasi-one-dimensional graphene nanoribbons (GNRs) synthesized is demonstrated by longitudinal unzipping carbon nanotubes (CNTs). The abundant functional groups on GNRs can absorb Ni atoms to form rich Ni–N4–C sites during the anchoring process, providing a high intrinsic activity. In addition, the GNRs, which maintain a quasi-one-dimensional structure and possess a high conductivity, interconnect with each other and form a conductive porous framework. The catalyst yields a 44 mA cm−2 CO partial current density and 96% faradaic efficiency of CO (FECO) at −1.1 V vs RHE in an H-cell. By adopting a membrane electrode assembly (MEA) flow cell, a 95% FECO and 2.4 V cell voltage are achieved at 200 mA cm−2 current density. This work provides a rational way to synthesize Ni SACs with a high Ni atom loading, porous morphology, and high conductivity with potential industrial applications.  相似文献   

11.
The CO2 reduction reaction (CO2RR) driven by renewable electricity represents a promising strategy toward alleviating the energy shortage and environmental crisis facing humankind. Cu species, as one type of versatile electrocatalyst for the CO2RR, attract tremendous research interest. However, for C2 products, ethanol formation is commonly less favored over Cu electrocatalysts. Herein, AuCu alloy nanoparticle embedded Cu submicrocone arrays (AuCu/Cu‐SCA) are constructed as an active, selective, and robust electrocatalyst for the CO2RR. Enhanced selectivity for EtOH is gained, whose Faradaic efficiency (FE) reaches 29 ± 4%, while ethylene formation is relatively inhibited (16 ± 4%) in KHCO3 aqueous solution. The ratio between partial current densities of EtOH and C2H4 (jEtOH/jC2H4) can be tuned in the range from 0.15 ± 0.27 to 1.81 ± 0.55 by varying the Au content of the electrocatalysts. The combined experimental and theoretical calculation results identify the importance of Au in modifying binding energies of key intermediates, such as CH2CHO*, CH3CHO*, and CH3CH2O*, which consequently modify the activity and selectivity (jEtOH/jC2H4) for the CO2RR. Moreover, AuCu/Cu‐SCA also shows high durability with both the current density and FEEtOH being largely maintained for 24 h electrocatalysis.  相似文献   

12.
Developing anode catalysts with substantially enhanced activity for hydrogen oxidation reaction (HOR) and CO tolerance performance is of great importance for the commercial applications of proton exchange membrane fuel cells (PEMFCs). Herein, an excellent CO-tolerant catalyst (Pd-WO3/C) has been fabricated by loading Pd nanoparticles on WO3 via an immersion-reduction route. A remarkably high power density of 1.33 W cm−2 at 80 °C is obtained by using the optimized 3Pd-WO3/C as the anode catalyst of PEMFCs, and the moderately reduced power density (73% remained) in CO/H2 mixed gas can quickly recover after removal of CO-contamination from hydrogen fuel, which is not possible by using Pt/C or Pd/C as anode catalyst. The prominent HOR activity of 3Pd-WO3/C is attributed to the optimized interfacial electron interaction, in which the activated H* adsorbed on Pd species can be effectively transferred to WO3 species through hydrogen spillover effect and then oxidized through the H species insert/output effect during the formation of HxWO3 in acid electrolyte. More importantly, a novel synergetic catalytic mechanism about excellent CO tolerance is proposed, in which Pd and WO3 respectively absorbs/activates CO and H2O, thus achieving the CO electrooxidation and re-exposure of Pd active sites for CO-tolerant HOR.  相似文献   

13.
This work reports a metal–organic framework (MOF) with less-coordinated copper dimers, which displays excellent electrochemical CO2 reduction (eCO2RR) performance with an advantageous current density of 0.9 A cm−2 and a high Faradaic efficiency of 71% to C2 products. In comparison with MOF with Cu monomers that are present as Cu1 O4 with a coordination number of 3.8 ± 0.2, Cu dimers exist as O3Cu1···Cu2O2 with a coordination number of 2.8 ± 0.1. In situ characterizations together with theoretical calculations reveal that two *CO intermediates are stably adsorbed on each site of less-coordinated Cu dimers, which favors later dimerization via a key intermediate of *CH2CHO. The highly unsaturated dual-atomic Cu provides large-quantity and high-quality actives sites for carbon–carbon coupling, achieving the optimal trade-off between activity and selectivity of eCO2RR to C2 products.  相似文献   

14.
Electrochemical reduction of CO to value-added products holds promise for storage of energy from renewable sources. Copper can convert CO into multi-carbon (C2+) products during CO electroreduction. However, developing a Cu electrocatalyst with a high selectivity for CO reduction and desirable production rates for C2+ products remains challenging. Herein, highly lattice-disordered Cu3N with abundant twin structures as a precursor electrocatalyst is examined for CO reduction. Through in situ activation during the CO reduction reaction (CORR) and concomitant release of nitrogen, the obtained metallic Cu° catalyst particles inherit the lattice dislocations present in the parent Cu3N lattice. The de-nitrified catalyst delivers an unprecedented C2+ Faradaic efficiency of over 90% at a current density of 727 mA cm−2 in a flow cell system. Using a membrane electrode assembly (MEA) electrolyzer with a solid-state electrolyte (SSE), a 17.4 vol% ethylene stream and liquid streams with concentration of 1.45 m and 230 × 10−3 m C2+ products at the outlet of the cathode and SSE-containment layer are obtained.  相似文献   

15.
Copper-based electrocatalysts effectively produce multicarbon (C2+) compounds during the electrochemical CO2 reduction (CO2RR). However, big challenges still remain because of the chemically unstable active sites. Here, cerium is used as a self-sacrificing agent to stabilize the Cu+ of CuS, due to the facile Ce3+/Ce4+ redox. CeO2-modified CuS nanoplates achieve high ethanol selectivity, with FE up to 54% and FEC2+ ≈ 75% in a flow cell. Moreover, in situ Raman spectroscopy and in situ Fourier-transform infrared spectroscopy indicate that the stable Cu+ species promote C C coupling step under CO2RR. Density functional theory calculations further reveal that the stronger *CO adsorption and lower C C coupling energy, which is conducive to the selective generation of ethanol products. This work provides a facile strategy to convert CO2 into ethanol by retaining Cu+ species.  相似文献   

16.
Despite enormous progress and improvement in photocatalytic CO2 reduction reaction (CO2RR), the development of photocatalysts that suppress H2 evolution reaction (HER), during CO2RR, remains still a challenge. Here, new insight is presented for controllable CO2RR selectivity by tuning the architecture of the photocatalyst. Au/carbon nitride with planar structure (p Au/CN) showed high activity for HER with 87% selectivity. In contrast, the same composition with a yolk@shell structure (Y@S Au@CN) exhibited high selectivity of carbon products by suppressing the HER to 26% under visible light irradiation. Further improvement for CO2RR activity was achieved by a surface decoration of the yolk@shell structure with Au25(PET)18 clusters as favorable electron acceptors, resulting in longer charge separation in Au@CN/Auc Y@S structure. Finally, by covering the structure with graphene layers, the designed catalyst maintained high photostability during light illumination and showed high photocatalytic efficiency. The optimized Au@CN/Auc/G Y@S structure displays high photocatalytic CO2RR selectivity of 88%, where the CO and CH4 generations during 8 h are 494 and 198 µmol/gcat., respectively. This approach combining architecture engineering and composition modification provides a new strategy with improved activity and controllable selectivity toward targeting applications in energy conversion catalysis.  相似文献   

17.
Electrocatalysis has emerged as an attractive way for artificial CO2 fixation to CH3OH, but the design and development of metal‐free electrocatalyst for highly selective CH3OH formation still remains a key challenge. Here, it is demonstrated that boron phosphide nanoparticles perform highly efficiently as a nonmetal electrocatalyst toward electrochemical reduction of CO2 to CH3OH with high selectivity. In 0.1 m KHCO3, this catalyst achieves a high Faradaic efficiency of 92.0% for CH3OH at ?0.5 V versus reversible hydrogen electrode. Density functional theory calculations reveal that B and P synergistically promote the binding and activation of CO2, and the rate‐determining step for the CO2 reduction reaction is dominated by *CO + *OH to *CO + *H2O process with free energy change of 1.36 eV. In addition, CO and CH2O products are difficultly generated on BP (111) surface, which is responsible for the high activity and selectivity of the CO2‐to‐CH3OH conversion process.  相似文献   

18.
It is a substantial challenge to construct electrocatalysts with high activity, good selectivity, and long-term stability for electrocatalytic reduction of carbon dioxide to formic acid. Herein, bismuth and indium species are innovatively integrated into a uniform heterogeneous spherical structure by a neoteric quasi-microemulsion method, and a novel C@In2O3@Bi50 core-shell structure is constructed through a subsequent one-step phase separation strategy due to melting point difference and Kirkendall effect with the nano-limiting effect of the carbon structure. This core-shell C@In2O3@Bi50 catalyst can selectively reduce CO2 to formate with high selectivity (≈90% faradaic efficiency), large partial current density (24.53 mA cm−2 at −1.36 V), and long-term stability (up to 14.5 h), superior to most of the Bi-based catalysts. The hybrid Bi/In2O3 interfaces of core-shell C@In2O3@Bi will stabilize the key intermediate HCOO* and suppress CO poisoning, benefiting the CO2RR selectivity and stability, while the internal cavity of core-shell structure will improve the reaction kinetics because of the large specific surface area and the enhancement of ion shuttle and electron transfer. Furthermore, the nano-limited domain effect of outmost carbon prevent active components from oxidation and agglomeration, helpful for stabilizing the catalyst. This work offers valuable insights into core-shell structure engineering to promote practical CO2 conversion technology.  相似文献   

19.
Simultaneously achieving high Faradaic efficiency, current density, and stability at low overpotentials is essential for industrial applications of electrochemical CO2 reduction reaction (CO2RR). However, great challenges still remain in this catalytic process. Herein, a synergistic catalysis strategy is presented to improve CO2RR performance by anchoring Fe‐N sites with cobalt phthalocyanine (denoted as CoPc©Fe‐N‐C). The potential window of CO Faradaic efficiency above 90% is significantly broadened from 0.18 V over Fe‐N‐C alone to 0.71 V over CoPc©Fe‐N‐C while the onset potential of CO2RR over both catalysts is as low as ?0.13 V versus reversible hydrogen electrode. What is more, the maximum CO current density is increased ten times with significantly enhanced stability. Density functional theory calculations suggest that anchored cobalt phthalocyanine promotes the CO desorption and suppresses the competitive hydrogen evolution reaction over Fe‐N sites, while the *COOH formation remains almost unchanged, thus demonstrating unprecedented synergistic effect toward CO2RR.  相似文献   

20.
In the face of the global energy challenge and progressing global climate change, renewable energy systems and components, such as fuel cells and electrolyzers, which close the energetic oxygen and carbon cycles, have become a technology development priority. The electrochemical oxygen reduction reaction (ORR) and the direct electrochemical carbon dioxide reduction reaction (CO2RR) are important electrocatalytic processes that proceed at gas diffusion electrodes of hydrogen fuel cells and CO2 electrolyzers, respectively. However, their low catalytic activity (voltage efficiency), limited long‐term stability, and moderate product selectivity (related to their Faradaic efficiency) have remained challenges. To address these, suitable catalysts are required. This review addresses the current state of research on Pt‐based and Cu‐based nanoalloy electrocatalysts for ORR and CO2RR, respectively, and critically compares and contrasts key performance parameters such as activity, selectivity, and durability. In particular, Pt nanoparticles alloyed with transition metals, post‐transition metals and lanthanides, are discussed, as well as the material characterization and their performance for the ORR. Then, bimetallic Cu nanoalloy catalysts are reviewed and organized according to their main reaction product generated by the second metal. This review concludes with a perspective on nanoalloy catalysts for the ORR and the CO2RR, and proposes future research directions.  相似文献   

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