Pd Clusters Loaded with Multivalent Cu Foam for Superior Electrochemical Nitrate Reduction and Selective N≡N Bond Formation.

The electrochemical denitrification of nitrate (NO3 -) in actual wastewater to nitrogen (N2) is an effective approach to reversing the current imbalance of the nitrogen cycle and the eutrophication of water. However, electrostatic repulsion between NO3 - and the cathode results in the low efficiency of NO3 - reduction reaction (NO3RR). Here, density functional theory (DFT) calculations are used as a theoretical guide to design a Pd cluster-loaded multivalent Cu foam (Pd/Cu2O-CF) electrocatalyst, which achieves a splendid 97.8% NO3 - removal rate, 97.9% N2 selectivity, 695.5 mg N g-1 Pd h-1 reduction efficiency, and 60.0% Faradaic efficiency at -1.3 V versus SCE. The projected density of states (pDOS) indicates that NO3 - and Pd/Cu2O-CF are bonded via strong complexation between the O 2p (in NO3 -) and Cu 3d (in Cu2O) with the input of voltage, which reduces the electrostatic repulsion and enhances the enrichment of NO3 - on the cathode. In-situ characterizations demonstrate that Pd[H] can reduce Cu2O to Cu, and subsequently Cu reduces NO3 - to nitrite (NO2 -) accompanied by in situ reconfiguration of multivalent Cu foam. NO2 - is then transferred to the surface of Pd clusters by the cascade catalysis and accelerates the breaking of N─O bonds to form Pd─N, and eventually achieves the N≡N bond formation.

Super-Assembled Hierarchical CoO Nanosheets-Cu Foam Composites as Multi-Level Hosts for High-Performance Lithium Metal Anodes.

Achieving uniform lithium (Li) deposition is the key to tackle uncontrollable dendrite growth, which hinders the application of Li metal anodes. In this study, molten Li is thermally injected into a 3D framework by growing lithiophilic CoO nanosheets on Cu foam (CF). The CoO layer grown on the CF surface physically adsorbs molten Li, which makes it possible to spontaneously wet the framework. The morphology of CoO nanosheets does not change during the Li injection process and formed a multi-level structure with the CF, which is difficult to be achieved previously, as most lithiophilic oxides undergo serious chemical changes due to chemical reaction with Li and cannot provide a stable submicron structure for the subsequent Li stripping/plating process. The super-assembled multi-level structure provides abundant Li nucleation sites and electrolyte/electrode contact areas for rapid charge transfer in the composite anode. Therefore, the prolonged lifespan of symmetrical cells for 300 cycles at 10 and 10 mAh cm-2 with lower polarization is achieved, which further renders the LiFePO4 and Li4 Ti5 O12 based full cells with improved capacity retention up to 87.3% and 80.1% after 500 cycles at 1 C. These results suggest that the composite anode has a great application prospect.

Effects of cathode coating materials and operational time on the mercury removal performance of electrokinetic remediation system for marine sediment.

Electrokinetic remediation (EK) is a promising in-situ technique for removing mercury (Hg) from contaminated sites; yet it demands long operational periods when conventional electrodes are used. Herein, we investigate the effectiveness of lab-prepared cathodes (Cu foam coated with reduced graphene oxide (rGO) or manganese oxide (MnO2)) to enhance Hg removal rates from sediment by EK. Although short term (2 h) Hg removal rates were insignificantly different (p-value > 0.05) when using the uncoated and coated Cu foam cathodes, long term (60 h) operations saw greater Hg removal by coated Cu foam cathodes over pure Cu foam, probably owing to the time required for Hg to migrate towards the electrodes from sediment. The highest Hg removal at the cathode was achieved when an αMnO2-coated Cu foam cathode was used with a strong-base anion exchange membrane (AEM) in the system. Using H3PO4, as a cathodic electrolyte resulted in a higher Hg removal efficiency than using NaCl and HCl electrolytes. Electromigration was found to be the dominant Hg-ions (e.g. HHgO2-, Hg2+) transport mechanism in the marine sediment during remediation. Overall, this research demonstrates that employing enhanced electrodes and AEMs can enhance Hg removal by EK processes in relatively shorter operating times than conventional EK processes.

3D Copper Foam-Supported CuCo2O4 Nanosheet Arrays as Electrode for Enhanced Non-Enzymatic Glucose Sensing.

CuCo2O4 anchored on Cu foam (CuCo2O4/CF) with polycrystalline features was fabricated by a mild process based on solvothermal reaction and subsequent calcination in this work. The structure and morphology of the obtained materials were thoroughly characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, and transmission electron microscopy. According to the above analysis, the morphology of the CuCo2O4 was nanosheet arrays. Meanwhile, the CuCo2O4 was grown on Cu foam successfully. The CuCo2O4/CF displayed good electrochemical properties for glucose detection at a linear range from 0 mM to 1.0 mM. Meanwhile, the detection limit was as low as 1 µM (S/N = 3), and the sensitivity was 20,981 µA·mM-1·cm-2. Moreover, the selectivity and the stability were tested with excellent results. This nanomaterial could show great potential application in electrochemical sensors.

Photoelectrocatalytic reduction of CO2 to methanol over a photosystem II-enhanced Cu foam/Si-nanowire system.

A solar-light double illumination photoelectrocatalytic cell (SLDIPEC) was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II (PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires (Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO2 conversion to methanol, with a high evolution rate (41.94mmol/hr), owing to fast electron transfer from PS-II to Cu foam. Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage (0.5V), and a suitable conduction band potential of Si (-0.6eV) allowed CO2 to be easily reduced to CH3OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO2 (8.03mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.

In situ growth of BiOBr on copper foam conductive substrate with enhanced photocatalytic performance.

Photocatalysis technology based on solar-powered semiconductors is widely recognized as a promising approach for achieving eco-friendly, secure, and sustainable degradation of organic contaminants. Nevertheless, conventional photocatalysts exhibit drawbacks such as a wide bandgap, and rapid recombination of photoinduced electron/hole pairs, in addition to complicated separation and recovery procedures. In this research, we cultivated BiOBr in situ on the surface of copper foam to fabricate a functional photocatalyst (denoted as BiOBr/Cu foam), which was subsequently employed for the photodegradation of Methylene Blue. Based on photodegradation experiments, the 0.3 BiOBr/Cu foam demonstrates superior photocatalytic efficacy compared to other photocatalysts under solar light irradiation. Furthermore, its ease of separation from the solution enhances its potential for reuse. The analysis of charge transfer revealed that the copper foam functions as an effective electron scavenger within the BiOBr/Cu foam, thereby facilitating charge separation and the generation of photo-induced holes. This phenomenon contributes to a significantly enhanced production of hydroxyl radicals. This study provides a valuable perspective on the design and synthesis of photocatalysts with heightened practicality, employing a conductive substrate.

Roughness Factors of Electrodeposited Nanostructured Copper Foams.

Copper-based electrocatalytic materials play a critical role in various electrocatalytic processes, including the electroreduction of carbon dioxide and nitrate. Three-dimensional nanostructured electrodes are particularly advantageous for electrocatalytic applications due to their large surface area, which facilitates charge transfer and mass transport. However, the real surface area (RSA) of electrocatalysts is a crucial parameter that is often overlooked in experimental studies of high-surface-area copper electrodes. In this study, we investigate the roughness factors of electrodeposited copper foams with varying thicknesses and morphologies, obtained using the hydrogen bubble dynamic template technique. Underpotential deposition (UPD) of metal adatoms is one of the most reliable methods for estimating the RSA of highly dispersed catalysts. We aim to illustrate the applicability of UPD of lead for the determination of the RSA of copper deposits with hierarchical porosity. To find the appropriate experimental conditions that allow for efficient minimization of the limitations related to the slow diffusion of lead ions in the pores of the material and background currents of the reduction of traces of oxygen, we explore the effect of lead ion concentration, stirring rate, scan rate, monolayer deposition time and solution pH on the accuracy of RSA estimates. Under the optimized measurement conditions, Pb UPD allowed to estimate roughness factors as high as 400 for 100 µm thick foams, which translates into a specific surface area of ~6 m2·g-1. The proposed measurement protocol may be further applied to estimate the RSA of copper deposits with similar or higher roughness.

Two-way rushing travel: Cathodic-anodic coupling of Bi2O3-SnO@CuO nanowires, a bifunctional catalyst with excellent CO2RR and MOR performance for the efficient production of formate.

Electrocatalytic carbon dioxide reduction reaction (CO2RR) generates high value-added products and simultaneously reduces excess atmospheric CO2 concentrations, is regarded as a potential approach to achieve carbon neutrality. However, the kinetic process of the anode oxygen evolution reaction (OER) is slow, resulting in a poor electrochemical efficiency of CO2RR. It is a breakthrough to replace OER with methanol oxidation reaction (MOR), which has more advantageous reaction kinetics. Herein, this work proposed a bifunctional catalyst Bi2O3-SnO modified CuO nanowires (Bi2O3-SnO@CuO NWs) with excellent CO2RR and MOR performance. For CO2RR, Bi2O3-SnO@CuO NWs achieved more than 90% formate selectivity at wide potential windows from -0.88 to -1.08 V (vs. reversible hydrogen electrode (RHE)), peaking at 96.6%. Meanwhile, anodic Bi2O3-SnO@CuO NWs achieved 100 mA cm-2 at a low potential of 1.53 V (vs. RHE), possessing nearly 100% formate selectivity ranging from 1.6 to 1.8 V (vs. RHE). Impressively, by coupling cathodic CO2RR and anodic MOR, the integrated electrolytic cell realized co-production of formate (cathode: 94.7% and anode: 97.5%), minimizing the energy input by approximately 69%, compared with CO2RR. This work provided a meaningful perspective for the design of bifunctional catalysts and coupling reaction systems in CO2RR.

Manipulation of the LiZn Alloy Process toward High-Efficiency Lithium Metal Anodes.

Synthesis of alloy-type materials (X) is one of the most effective approaches to limit lithium dendrites in Li metal anode (LMA) because of their satisfactory lithiophilicity and easy electrochemical reaction with lithium. However, current investigations have only focused on the influence of the resulting alloyed products (LiX) on the properties of LMA, but the alloying reaction process between Li+ and X has been mostly ignored. Herein, by masterly taking advantage of the alloying reaction process, a novel approach is developed to more effectively inhibit lithium dendrites than the conventional strategy that just considers the utilization of alloyed products LiX. A three-dimensional substrate material loaded with metallic Zn on the surface of Cu foam is synthesized by a simple electrodeposition process. During Li plating/stripping, both alloy reaction processes between Li+ and Zn and LiZn product are involved, which makes the disordered Li+ flux near the substrate first react with Zn metal and then results in an even Li+ concentration for more uniform Li nucleation and growth. The full cell (Li-Cu@Zn-15//LFP) exhibits the reversible capacity of 122.5 mAh g-1, and a high capacity retention of 95% is achieved after 180 cycles. This work proposes a valuable concept for the development of alloy-type materials in energy storage devices.

3D Porous Cu-Composites for Stable Li-Metal Battery Anodes.

Lithium (Li) metal is a promising anode material for lithium-ion batteries (LIBs) because of its high theoretical specific capacity of 3860 mAh g-1 and the low potential of -3.04 V versus the standard hydrogen electrode (SHE). However, these anodes rely on repeated plating and stripping of Li, which leads to consumption of Li inventory and the growth of dendrites that can lead to self-discharge and safety issues. To address these issues, as well as problems related to the volume change of these anodes, a number of different porous conductive scaffolds have been reported to create high surface area electrode on which Li can be plated reliably. While impressive results have been reported in literature, current processes typically rely on either expensive or poorly scalable techniques. Herein, we report a scalable fabrication method to create robust 3D Cu anodes using a one-step electrodeposition process. The areal loading, pore structure, and electrode thickness can be tuned by changing the electrodeposition parameters, and we show how standard mechanical calendering provides a way to further optimize electrode volume, capacity, and cycling stability. Optimized electrodes achieve high Coulombic efficiencies (CEs) of 99% during 800 cycles in half cells at a current density of 0.5 mA cm-2 with a total capacity of 0.5 mAh cm-2. To the best of our knowledge, this is the highest value ever reported for a host for Li-metal anodes using lithium bis(trifluoromethanesulfonyl)imide LITFSI based electrolyte.

Three-Dimensional Octahedral Nanocrystals of Cu2O/CuF2 Grown on Porous Cu Foam Act as a Lithophilic Skeleton for Dendrite-Free Lithium Metal Anode.

Metallic-lithium (Li) anodes are highly sought-after for next-generation energy storage systems due to their high theoretical capacity and low electrochemical potential. However, the commercialization of Li anodes faces challenges, including uncontrolled dendrite growth and volume changes during cycling. To address these issues, we developed a novel three-dimensional (3D) copper current collector. Here, we propose a two-step method to fabricate Cu2O/CuF2 octahedral nanocrystals (ONCs) onto 3D Cu current collectors. The resulting Cu foam with distributed ONCs provides active electrochemical sites, promoting uniform Li nucleation and dendrite-free Li deposition. The stable Cu2O/CuF2 ONCs@CF metallic current collector serves as a reliable host for dendrite-free lithium metal anodes. Additionally, the highly porous copper foam with a preconstructed conductive framework of Cu2O/CuF2 ONCs@CF effectively reduces local current density, suppressing volume changes during Li stripping and plating. The symmetric cell using Cu2O/CuF2 ONCs@CF metallic current collector exhibits excellent stability, maintaining over 1600 h at 1 mA cm-2 and a highly stable Coulombic efficiency of 98% over 100 cycles at the same current density, outperforming Li@CuF metallic current collectors. Furthermore, in a full-cell configuration paired with nickel-rich layered oxide cathode materials (Li@Cu2O/CuF2 ONCs@CF//NMC-811), the proposed setup demonstrates exceptional rate performance and an extended cycle life. In conclusion, our work presents a promising strategy to address Li anode challenges and highlights the exceptional performance of the Cu2O/CuF2 ONCs@CF metallic current collector, offering potential for high-capacity and long-lasting lithium-based energy storage systems.

Amorphous-Amorphous Coupling Enhancing the Oxygen Evolution Reaction Activity and Stability of the NiFe-Based Catalyst.

Efficient and stable electrocatalytic water splitting plays a critical role in energy storage and conversion but is strongly restricted by the low activity and stability of catalysts associated with the complicated oxygen evolution reaction (OER). This work provides a strategy to fabricate an advanced NiFe-based catalyst to steadily speed up the OER based on a strong amorphous-amorphous coupling effect generated through amorphous CuS that induces the formation of amorphous NiFe layered double hydroxide (LDH) nanosheets (A-NiFe NS/CuS). The presence of the strong coupling effect not only modifies the electronic structure of catalytic sites to accelerate the reaction kinetics but also enhances the binding between the catalyst and substrate to strengthen the durability. In comparison to well-grown core-shell crystalline NiFe LDH on CuO, the as-synthesized amorphous A-NiFe NS/CuS gives a low overpotential of 240 mV to achieve 100 mA cm-2 and shows robust stability under 100 h of operation at the same current density. Therefore, amorphous-amorphous coupling between catalyst-substrate by elaborate and rational engineering yields an opportunity to design efficient and robust NiFe-based OER catalysts.

Polyethyleneimine-reinforced Sn/Cu foam dendritic self-supporting catalytic cathode for CO2 reduction to HCOOH.

In this work, a novel catalytic cathode of polyethyleneimine (PEI)-Sn/Cu foam with dendritic structure was prepared by electrodeposition and impregnation. It was used in the electrocatalytic reduction of CO2 to HCOOH, and its performance in this process was evaluated. At -0.97 V vs. RHE, the faradaic efficiency and current density reached 92.3% and 57.1 mA cm-2, respectively, in a 0.5 M KHCO3 electrolyte. The HCOOH production rate reached 890.4 µmol h-1 cm-2, which exceeds those for most reported Sn catalysts. Density functional theory calculations showed that use of Sn/Cu foam is more conducive to HCOOH formation than use of Cu or Sn alone, and *OCHO is the main intermediate in HCOOH formation. The results of OH- adsorption experiments confirmed that the introduction of PEI enhanced the catalytic capacity of the Sn/Cu foam, stabilized CO2·- intermediates, and promoted HCOOH generation. These results will provide an attractive strategy for developing efficient catalysts with excellent activities and stabilities for CO2 electroreduction.

Binder free 3D core-shell NiFe layered double hydroxide (LDH) nanosheets (NSs) supported on Cu foam as a highly efficient non-enzymatic glucose sensor.

Rational design with fine-tuning of the electrocatalyst material is vital for achieving the desired sensitivity, selectivity, and stability for an electrochemical sensor. In this study, a three-dimensional (3D) hierarchical core-shell catalyst was employed as a self-standing, binder-free electrode for non-enzymatic glucose sensing. The catalyst was prepared by decorating the shell of NiFe layered double hydroxide (LDH) nanosheets (NSs) on the core of Cu nanowires (NWs) grown on a Cu foam support. The optimized 3D core-shell Cu@NiFe LDH sensor demonstrated higher sensitivity (7.88 mA mM-1cm-2), lower limit of detection (0.10 µM) and wider linear range (1 µM to 0.9 mM) in glucose sensing with a low working potential (0.4 V). The applied sensor also showed excellent stability, reproducibility, interference ability as well as practicability in real environment. The detection of real samples further suggests its great feasibility for practical applications. The superior electrocatalytic performance is collectively ascribed to the excellent electro-conductivity of the Cu substrate, the distinct self-standing 3D porous nanostructure, the ultrathin homogenous architecture, and the appropriate loading amount of NiFe LDH NSs. This study then provides a non-enzymatic glucose sensor with 3D Cu@NiFe LDH electrode for ultrahigh sensitivity and stability.

Design and Construction of Cu(OH)2/Ni3S2 Composite Electrode on Cu Foam by Two-Step Electrodeposition.

A Cu(OH)2/Ni3S2 composite has been designed and in situ constructed on Cu foam substrate by facile two-step electrodeposition. Cu(OH)2 is achieved on Cu foam by galvanostatic electrodeposition, and the subsequent coating of Ni3S2 is realized by cyclic voltammetric (CV) electrodeposition. The introduction of Cu(OH)2 provides skeleton support and a large specific surface area for the Ni3S2 electrodeposition. Benefiting from the selection of different components and preparation technology, the Cu(OH)2/Ni3S2 composite exhibits enhanced electrochemical properties with a high specific capacitance of 4.85 F cm-2 at 2 mA cm-2 and long-term cyclic stability at 80.84% (4000 cycles).

Dimensionally Stable Composite Li Electrode with Cu Skeleton and Lithophilic Li-Mg Alloy Microstructure.

Lithium electrodes have gained increasing attention in recent years for their promising applications in high-energy-density secondary batteries. However, structural instability during cycling remains a considerable obstacle to development. In this study, a dimensionally stable Li-Mg/Cu composite electrode was fabricated. Cu foam as a plate grid can sustain the structure, and Li-Mg alloy as the active and lithophilic component can guide the uniform Li plating within the composite. Thus, Li-Mg/Cu electrode shows long-term stability in terms of dimensional change and surface morphology. This work provides a facile and practical way to fabricate composite Li electrodes with high dimensional stability for secondary batteries.

Electrosynthesis of Vertically Aligned Zinc Oxide Nanoflakes on 3D Porous Cu Foam Enables Dendrite-Free Li-Metal Anode.

Three dimensional (3D) hosts have been recognized as effective current collectors for Li metal anodes because of their physical suppression of the lithium dendrites growth. A lithiophilic surface layer on them could increase the Li metal nucleation sites, further regulating the genuine plating of Li metal. The current strategies to construct this lithiophilic layer on 3D structure is complex and not suitable for the scalable fabrication of Li metal anode. In this work, we developed a facile method to grow vertically aligned ZnO nanoflakes on the surface of 3D Cu foam through an electrochemical synthetic process, which physically suppressed the Li dendrites growth due to the unique structure during the Li plating/stripping process. Moreover, these lithiophilic flakes effectively increase the specific surface area of the anode and Li metal nucleation sites number, which reduces the local current densities, leading to the formation of a robust SEI and further suppressing the Li dendrites growth. Consequently, the performances of the symmetric Li plated Cu foam/Li cell and the Li plated Cu foam/LiFePO4 full cell have been greatly enhanced after the growth of vertically aligned ZnO nanoflakes on the Cu foam surface, including capacity, cycling stability, overpotential, and rate capability.

3D Hierarchical Nanocrystalline CuS Cathode for Lithium Batteries.

Conductive and flexible CuS films with unique hierarchical nanocrystalline branches directly grown on three-dimensional (3D) porous Cu foam were fabricated using an easy and facile solution processing method without a binder and conductive agent for the first time. The synthesis procedure is quick and does not require complex routes. The structure and morphology of the as-deposited CuS/Cu films were characterized by X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy and transmission electron spectroscopy, respectively. Pure crystalline hexagonal structured CuS without impurities were obtained for the most saturated S solution. Electrochemical testing of CuS/Cu foam electrodes showed a reasonable capacity of 450 mAh·g-1 at 0.1 C and excellent cyclability, which might be attributed to the unique 3D structure of the current collector and hierarchical nanocrystalline branches that provide fast diffusion and a large surface area.

A Novel 3D Hierarchical Plasmonic Functional Cu@Co3O4@Ag Array as Intelligent SERS Sensing Platform with Trace Droplet Rapid Detection Ability for Pesticide Residue Detection on Fruits and Vegetables.

Rapid and effective detection of pesticide residues from complex surfaces of fruits and vegetables has important significance. Herein, we report a novel three-dimensional (3D) hierarchical porous functional surface-enhanced Raman scattering (SERS) substrate, which is fabricated by successive two-step hydrothermal synthesis strategy of silver nanoparticles (Ag NPs) and cobalt oxide nanowires (Co3O4 NWs) on the 3D copper foam framework as Cu@Co3O4@Ag-H. The strategy offers a new avenue for localized plasmonic materials distribution and construction, which exhibits better morphology regulation ability and SERS activity (or hotspots engineering) than physical spurring obtained Cu@Co3O4@Ag-S. The developed Cu@Co3O4@Ag-H possesses large surface area and rich hotspots, which contributes to the excellent SERS performance, including homogeneity (RSD of 7.8%), sensitivity (enhancement factor, EF of 2.24 × 108) and stability. The Cu@Co3O4@Ag-H not only provides plenty of Electromagnetic enhancement (EM) hotspots but also the trace detection capability for droplet rapid sensing within 2 s. Cu@Co3O4@Ag-H substrate is further developed as an effective SERS sensing platform for pesticide residues detection on the surfaces of fruits and vegetables with excellent LOD of 0.1 ppm, which is lower than the most similar reported works. This work offers new potential for bioassay, disease POCT diagnosis, national security, wearable flexible devices, energy storage and other related fields.

The Optical and Electrical Performance of CuO Synthesized by Anodic Oxidation Based on Copper Foam.

Metal oxide semiconductor materials have a wide range of applications in the field of solar energy conversion. In this paper, CuO was prepared directly on copper foam substrate by anodic oxidation. The effects of current density and anodizing temperature on sample preparation and performance were studied. Field emission scanning electron microscopy (FESEM) and X-ray diffractometer (XRD) had been used to determine the morphology and phase structure of the sample, and its optical and electrical properties were discussed through UV-vis spectrophotometer and electrochemical tests. In addition, the influences of experimental conditions such as current density and reaction temperature on the morphology and properties of CuO were systematically discussed. The FESEM images showed that as the anodic oxidation temperature increase, the morphology of the prepared sample changed from nanowires to leaf-like CuO nanosheets. According to the results of XRD, the structure of prepared CuO was monoclinic, and the intensity of diffraction peaks gradually increased as anodizing temperature increased. We found that the optimum current density and anodizing temperature were 20 mA cm-2 and 60 °C, respectively. The results of electrochemical indicated that the CuO electrode based on copper foam (CuO/Cu foam) prepared at the optimum exhibited the highest specific capacitance (0.1039 F cm-2) when the scan rate was 2 mV s-1.