Cu-Co Alloys Research Articles

Tunning valence state of cobalt centers in Cu/Co-CoO1-x for significantly boosting water-gas shift reaction

Dual active sites with synergistic valence state regulation under oxidizing and reducing conditions are essential for catalytic reactions with step-wise mechanisms to modulate the complex adsorption sites of reactant molecules on the surfaces of heterogeneous catalysts with maximized catalytic performances, but it has been rarely explored. In this work, uniformly dispersed CuCo alloy and CoO nanosheet composite catalysts with dual active sites are constructed, which shows huge boost in activity for catalyzing water-gas shift reaction (WGSR), with a record high reaction rate reaching 204.2 μmolCO gcat.−1 s−1 at 300 °C for Cu1Co9Ox amongst the reported Cu-based and Co-based catalysts. A synergistic mechanism is proposed that Coδ+ species can be easily reduced by CO adsorbed on Cu and Co0 can be oxidized by H2O. Systematic in situ characterization results reveal that the addition of Cu can regulate the redox properties of Co species and thus modulate the adsorption properties of catalysts. Particularly, doping of Cu0 sites weakens the affinity of the surface to CO or CO2 to a moderate level. Moreover, it also promotes the oxidation of *CO to *COOH and the desorption of the product CO2, reducing the carbon poisoning of the catalyst and thus increasing the reactivity. The results would provide guidance for the construction of novel heterogeneous catalyst with dual active sites and clarify its underlying reactivity enhancement mechanism induced by the tunning of valence state of metal centers for heterogeneous catalytic reactions.

Machine Learning Boosted Entropy-Engineered Synthesis of CuCo Nanometric Solid Solution Alloys for Near-100% Nitrate-to-Ammonia Selectivity.

Nanometric solid solution alloys are utilized in a broad range of fields, including catalysis, energy storage, medical application, and sensor technology. Unfortunately, the synthesis of these alloys becomes increasingly challenging as the disparity between the metal elements grows, due to differences in atomic sizes, melting points, and chemical affinities. This study utilized a data-driven approach incorporating sample balancing enhancement techniques and multilayer perceptron (MLP) algorithms to improve the model's ability to handle imbalanced data, significantly boosting the efficiency of experimental parameter optimization. Building on this enhanced data processing framework, we developed an entropy-engineered synthesis approach specifically designed to produce stable, nanometric copper and cobalt (CuCo) solid solution alloys. Under conditions of -0.425 V (vs RHE), the CuCo alloy exhibited nearly 100% Faraday efficiency (FE) and a high ammonia production rate of 232.17 mg h-1 mg-1. Stability tests in a simulated industrial environment showed that the catalyst maintained over 80% FE and an ammonia production rate exceeding 170 mg h-1 mg-1 over a testing period of 120 h, outperforming most reported catalysts. To delve deeper into the synergistic interaction mechanisms between Cu and Co, in situ Raman spectroscopy was utilized for real-time monitoring, and density functional theory (DFT) calculations further substantiated our findings. These results not only highlight the exceptional catalytic performance of the CuCo alloy but also reflect the effective electronic and energy interactions between the two metals.

A‐Site Defect Engineering Regulates Bimetallic Exsolution in Perovskite Oxide Boosting the Performance of Li–O2 Batteries

AbstractThe application life of Lithium–oxygen (Li–O2) batteries can be significantly affected by the formation and full decomposition of the discharge product Li2O2. After exsolution, the catalyst is designed to control the morphology and crystallinity of Li2O2 enhanced reversibility. In the perovskite exsolution system, the large amount of A‐site defects are introduced to induce the activation of lattice oxygen and the formation of oxygen vacancy, and promote the bimetallic exsolution from LaxFe0.8Cu0.1Co0.1O3. When x = 0.70, the distribution density of CuCo alloy and Cu metal increases and the size is smaller. Through exsolution process, the resulting oxygen vacancy and more doped ions exsolved expose a significant number of active sites that enhance the charge transfer and catalytic activity. Therefore, the charge resistance (Rct) smaller and can be better decomposed due to the generated small‐size Li2O2 with nano‐sheet morphology. Meanwhile, theoretical calculation shows that the exsolution of the catalyst enhances the adsorption of the intermediate LiO2 that makes the surface mechanism more advantageous. The reversibility of the battery is improved, and the cycle stability reaches 195 cycles. This work can serve as a guide for the development of exsolution that directs the design of high efficiency cathode catalyst.

Active Sites on the CuCo Catalyst in Higher Alcohol Synthesis from Syngas: A Review

Higher alcohol synthesis through the Fischer–Tropsch (F–T) process was considered a promising route for the efficient utilization of fossil resources could be achieved. The CuCo catalysts were proven to be efficient candidates and attracted much interest. Great efforts have been made to investigate the active sites and mechanisms of CuCo catalysts. However, the industrialized application of CuCo catalysts in this process was still hindered. The poor stability of this catalyst was one of the main reasons. This short review summarized the recent development of active sites on the CuCo catalysts for higher alcohol synthesis, including CuCo alloy particles, CuCo core–shell particles, and unsaturated particles. The complex active sites and their continual changes during the reaction led to the poor stability of the catalysts. The effect of active sites on catalytic performance was discussed. Furthermore, the key factors in fabricating stable CuCo catalysts were proposed. Finally, reasonable proposals were proposed for designing efficient and stable CuCo catalysts in higher alcohol synthesis.

Structure effect of ENPs on mechanical properties of amorphous CuCo alloys

Nanoparticles play an important role in the properties of metallic glasses (MGs) due to their diversified structures; however, their structure–property relationship is unclear. In this paper, three ex situ metallic glass matrix composites were assembled by three kinds of nanoparticles and Cu50Co50 MG obtained by rapid cooling, and their structural evolution under uniaxial compression is investigated by molecular dynamic simulation. It is found that the activated atoms always preferentially accumulate in the amorphous region near the embedded nanoparticles (ENPs). ENPs hinder the propagation of shear bands and lead to strain-hardening behavior. The fractal structures convert the HCP and tDh atoms into atoms of other structures to improve the anti-deformation ability, and the parallel-twin structure improves the anti-deformation ability through the mutual conversion of the FCC and HCP atoms. These findings provide a new idea for improving the mechanical properties of MGs. The change in the ENP structure provides theoretical support for the design of composite materials with specific requirements for structural evolution.

Abnormal resistivity behavior of Co–Cu alloys and responsible metastable liquid phase separation

The electrical resistivity of Co-Cu alloys with Cu content of 10, 20, 30, 40, 50, 60, 70, 80, and 90 at.% was measured in the temperature range from 1400 to 2100K. The experiments were performed during of heating and subsequent cooling of the samples. For alloys with Cu content of 30, 40, 60, 70, 80, and 90 at.%, a bend in the cooling curve specific to the liquid-liquid phase separation (LLPS) process was observed. LLPS is shown when the melt is undercooled to the binodal temperature T∗. The phase transition model of LLPS was proposed for to theoretically determine the temperatures T∗. The LLPS model demonstrates the possibility of percolation phenomena occurring in Cu-Co heterogeneous melts rich in cobalt. The LLPS model shows good agreement with experimental data and the abnormal resistivity behavior of Co–Cu alloys.

Fabrication of CoM (M= Ni, Cu) alloys modified carbon electrocatalysts by pyrolysis of dual-metal-site metal-organic frameworks for efficient dye-sensitized solar cells

The regulation of interface properties of multi-component transition metals in carbon-based catalyst has been an effective method to boost the electrochemical performance of counter electrode (CE) catalysts for dye-sensitized solar cells (DSSCs). Herein, CoNi-metal-organic framework (MOF) and CoCu-MOF are fabricated through introducing Ni and Cu into the stable Co-MOF, and used as sacrificial precursor in the followed pyrolysis-alloying process. And then, the target product CoM (M=Ni, Cu)/N-doped polyhedron-like carbon (NC) are successfully obtained, in which CoNi and CoCu alloy nanoparticles are uniformly dispersed on the N-doped carbon skeleton. Such MOFs-derived carbon matrix can not only supply as conductive network, but also isolate the alloy nanoparticles to avoid agglomeration, ensuring more effective active sites. Meanwhile, the built-in electric field generated by the Mott-Schottky interface effect of CoM/NCs could regulate the electronic structure inside the catalysts, resulting in faster electron transfer ability. Significantly, the reduced work function due to the introduction of Cu atoms leads to stronger self-driven electron transfer at the heterogeneous interface of CoCu/NC, which helps to improve reaction activity and electrocatalytic efficiency. Among the tested catalysts, CoCu/NC displays a more satisfying power conversion efficiency (PCE) of 7.60 % when assembled into CE of DSSC, also superior to 7.19 % of Pt.

Facile and fast fabrication of CuCo alloy and N-codoped hierarchical porous carbon catalyst for efficient oxygen reduction reaction in microbial fuel cells

Designing a low-cost, high-performance oxygen reduction reaction (ORR) catalyst to replace the precious metal catalyst remains a huge challenge for microbial fuel cells (MFCs). Herein, a facile and rapid approach to fabricate highly active N-doped hierarchical porous carbon (NHPC) supported bimetal CuCo/NHPC composites with densely accessible active sites is developed by pyrolysis of Cu-doped ZIF-67 (CuCo-ZIF) precursor. In which, CuCo-ZIF precursor is synthesized through a one-pot hydrothermal method. Results showed that in addition to create additional Cu-Nx sites and increase N content, the Cu doping induces a hierarchical porous structure CuCo/NHPC composite with pores centered around 2.4, 4.2 nm and 10–60 nm, which can significantly accelerate the mass/electron transfer and improve efficient utilization of the active sites. The resulting CuCo/NHPC composite provides abundant active sites, high content of pyridinic-N and graphitic-N, which significantly boosts ORR performances. The CuCo/NHPC-T with pyrolysis temperature of 800 °C achieves remarkable ORR activity with low charge transfer resistances, high half-wave potential. The MFC assembled with CuCo/NHPC-800 (774.2 mW·m−2 and 0.713 V) significantly outperforms MFC assembled with Co-NC-800 (541.9 mW·m−2 and 0.583 V) in terms of maximum power density and open-circuit voltage. Moreover, the output voltage of MFC assembled with CuCo/NHPC-800 exhibited no significant downward trend within 30 days, which was better than that of Pt/C catalyst. This work provides a feasible time-saving route to develop promising nitrogen-enriched mesoporous carbon bimetallic ORR catalysts.

Silica Confinement for Stable and Magnetic Co-Cu Alloy Nanoparticles in Nitrogen-Doped Carbon for Enhanced Hydrogen Evolution.

Ammonia borane (AB) with 19.6 wt % H2 content is widely considered a safe and efficient medium for H2 storage and release. Co-based nanocatalysts present strong contenders for replacing precious metal-based catalysts in AB hydrolysis due to their high activity and cost-effectiveness. However, precisely adjusting the active centers and surface properties of Co-based nanomaterials to enhance their activity, as well as suppressing the migration and loss of metal atoms to improve their stability, presents many challenges. In this study, mesoporous-silica-confined bimetallic Co-Cu nanoparticles embedded in nitrogen-doped carbon (CoxCu1-x@NC@mSiO2) were synthesized using a facile mSiO2-confined thermal pyrolysis strategy. The obtained product, an optimized Co0.8Cu0.2@NC@mSiO2 catalyst, exhibits enhanced performance with a turnover frequency of 240.9 molH2 ⋅ molmetal ⋅ min-1 for AB hydrolysis at 298 K, surpassing most noble-metal-free catalysts. Moreover, Co0.8Cu0.2@NC@mSiO2 demonstrates magnetic recyclability and extraordinary stability, with a negligible decline of only 0.8 % over 30 cycles of use. This enhanced performance was attributed to the synergistic effect between Co and Cu, as well as silica confinement. This work proposes a promising method for constructing noble-metal-free catalysts for AB hydrolysis.

Electrocatalytic reduction of CO2 by Co-Cu metastable alloy nanoparticles derived from MOFs

The construction of non-noble metal electrodes for the catalytic reduction of CO2 has drawn much attention in recent years. Herein, a facile CoCu@C composite catalyst was synthesized by simply carbonizing CoCu-MOFs, a bimetal MOFs fabricated by integrating Cu2+ ions into the synthesis of ZIF-67. Co-Cu alloy nanoparticles were closely embedded in porous carbon skeleton. Notably, the optimal Co1Cu3@C sample exhibited a total catalytic current of 29.8 mA·cm−2 at −0.7 V vs RHE, which was 2.56 times of the Co@C catalyst derived from original ZIF-67. Besides, the Co1Cu3@C sample achieved targeted CO:H2 ratios in the CO2 reduction reactions, covering approximately 1:1.7–1:4, meeting well with industrial needs. Density Functional Theory (DFT) calculations unveiled an electron migration from Co to Cu within the alloy, indicating the promoted transfer of electrons. Co atoms in Co-Cu alloy was found as the predominant active sites for the reduction of CO2. The study provided a economical CO2 reduction electrocatalyst with cheap feedstock, low operating voltage and specific ratio of syngas. Additionally, this work significantly advances our understanding of Co-Cu alloy electrocatalysts, providing crucial insights for the ongoing evolution of electrocatalyst research in material preparation and theoretical calculations.

Highly active CeO2-CuCo nanoparticles supported on hollow N-doped carbon spheres for boosting ammonia borane hydrolysis and tandem 4-nitrophenol reduction reactions

It’s a safe method to use high hydrogen density ammonia borane (AB) to facilitate the tandem hydrogenation of aromatic nitro compounds. While a major problem for tandem hydrogenation, the development of non-noble metal catalysts with high activity and stability is encouraging. This work involved the synthesis of highly active CeO2/CuCo nanoparticles support on hollow N-doped carbon spheres and its investigation for AB hydrolysis, taking into account the impacts of the HNCSs and CeO2 supports. Because CuCo alloy, CeO2, and HNCSs supports worked in concert, HNCSs@CeO2/CuCo was found to be the best catalyst. The activation energy achieved was comparable to the reported Pd- and Pt-based catalysts, with a value as low as 21.8 kJ/mol. Using AB as the in-situ H2 source, HNCSs@CeO2/CuCo exhibited a significant degree of activity in the one-pot tandem reduction of 4-NP with the turnover frequency of 2830.2 h−1, even surpassing over ten times of some noble metal catalysts. Following five consecutive cycles of reaction condition tuning, the HNCSs@CeO2/CuCo catalyst demonstrated a constant conversion efficiency. Also, the catalyst's uses for one-pot tandem reduction of other highly active aromatic nitro compounds were expanded.

Production of jet fuel cycloalkanes from 5‐(hydroxymethyl)furfural via cascade catalysis on Mg(Al)(Zr)O supported CuCo

AbstractCatalytic conversion of biomass‐derived 5‐(hydroxymethyl)furfural (5‐HMF) into carbon‐increased hydrocarbons as drop‐in energy‐rich biofuels has received a great deal of concern for the development of sustainable chemical industry. Here, we demonstrate a one‐pot conversion of 5‐HMF into C9‐alkanes on one single catalyst, acidic–basic layered double oxides (Mg(Al)(Zr)O) supported CuCo alloy. The well‐defined multifunctional catalytic sites with harmonious combination carry out cascade catalysis, affording C9‐alkanes (including 30% of more value‐added branched‐cycloalkanes) in 83% yield. The basic–acidic sites on Mg(Al)(Zr)O show high activity for aldol condensation of 5‐HMF and acetone, producing 4‐[5‐(hydroxymethyl)‐2‐furanyl]‐3‐buten‐2‐one (HAc) in a yield of >99%. The engineered Co–Cu–Co linkages on supported CuCo perform efficient hydrodeoxygenation, affording C9‐alkanes in a selectivity of 96% from HAc. C9‐cycloalkanes are generated from the cyclization of the corresponding monohydric alcohol intermediates by the synergy of acidic and CuCo sites in the hydrodeoxygenation reaction.

Pulsed electrodeposition of homogenous and heterogeneous solid solution layered structure in high strength nanocrystalline Co[sbnd]Cu alloys

A supersaturated solid solution nanostructure of an immiscible CoCu system is among the promising nanocrystalline (NC) alloys offering enhanced thermal and mechanical stability. In this paper, experiments were conducted to study the phase transformation and tailoring microstructure from a homogeneous/single-phase to a heterogeneous/dual-phase solid solution layered CoCu nanostructure via pulsed electrochemical deposition (PED). The increasing concentration of sodium dodecyl sulfate (SDS) in electrolyte played a crucial role in stabilizing a homogeneous solid solution CoCu nanostructure. On the other hand, the opposite approach led to the formation of heterogeneous solid solution CoCu alloys in the form of multilayered nanostructure consisting of the primary and secondary solid solution CoCu differing in 10–15 at.% Cu. The separation of primary and secondary phase is more prominent with the extended pulsed periods. The mechanical properties of selected single- and dual-phase alloys were investigated through micro-pillar compression, revealing that a combination of a high yield strength and an elevated strain hardening can be achieved in NC materials through a combined solid solution strengthening and hardening through nano-twin (NT).

Hydrodeoxygenation of furfural to 2-methylfuran over Cu-Co confined by hollow carbon cage catalyst enhanced by optimized charge transfer and alloy structure

Hydrodeoxygenation of furfural over non-noble metal catalyst is an effective route to synthesis 2-methylfuran, but the reaction is often hampered by the low activity and selectivity of the catalyst. Herein, a bimetallic catalyst with CuCo alloy encapsulated in a hollow nitrogen-doped carbon cages (CuCo/NC) are fabricated by using ZIF-67 as a sacrificial template, which exhibited superior catalytic performance and a full conversion of furfural with a 95.7 % selectivity towards 2-methylfuran was achieved at an under relatively mild reaction conditions (150 ℃, 1.5 MPa H2 and 4.0 h). The characterizations and density functional theory calculations clearly evidenced that the introduced Cu species acts as a switch to regulate the activity and selectivity of the catalyst via two aspects. On the one hand, the Cu species perturb the Co electronic structure leading to adsorption configuration of furfural change from flat to vertical on the catalyst surface, which successfully hindered the hydrogenation of furan ring, resulting high selectivity towards 2-methylfuran. On the other hand, the formed CuCo (111) sites promotes the dissociation of hydrogen, cleavage of the CO bond and reduces the diffusion barrier of hydrogen so as to advance the formation of 2-methylfuran. This work may provide a feasible strategy for the design of nanoalloy catalyst for the hydrodeoxygenation of biomass platforms to value-added chemicals.

Investigating hydrodeoxygenation of furfural for 2-methylfuran production over Cu-Mo/CoOx catalyst: Influence of Mo promoter

Catalytic conversion of furfural (FF) into 2-methylfuran (2-MF) has received great attention, in which the control of catalytic selectivity plays a crucial issue. The design of efficient catalysts based on non-noble metals is still a huge challenge for this transformation. Herein, transition metal oxide CoOx supported Cu catalysts have been prepared via a simple sol–gel route and applied in this transformation. A significantly enhanced 2-MF selectivity have been achieved when Mo was used as an additive during preparation. Under mild conditions (180 °C and 2 MPa H2), the conversion of FF exceeds 99% and 2-MF yield was up to 92% over the Cu-Mo/CoOx with the molar ratio of Cu/Mo is 3. Characterization results demonstrated that the addition of Mo not only accelerated the formation of CuCo alloy in the catalyst, but also enhanced the electropositivity of Coδ+ due to the electron transfer from Co to Mo, which then affected the adsorption mode of C = O from η1-(O) to η2-(C, O). Consequently, this adsorption configuration and abundant Lewis acid sites on Cu-Mo/CoOx facilitates the C-O cleavage, giving rise to the production of 2-MF. In addition, Cu-Mo/CoOx also exhibits good stability during the recycle experiment.

Electrochemical recycling of diamond and precious metals from used diamond tools

The recycling of used diamond tools, which contain a large amount of unused diamond particles and precious metals, can not only realize the reuse of resources, but also reduce the pressure of environmental protection. In this paper, diamond particles were recovered by acid dissolution of aqua regia, and the current density, complexing agent concentration and pH value of the acid dissolution system were adjusted to recover Cu and Co by electrodeposition. Scanning electron microscope and energy spectrometer were used to study the changes of the composition and morphology of the plated layers, and the effects of the parameters such as current density, complexing agent concentration and pH on the organization and composition of the alloy plated layers were analyzed. The results showed that at the current density of 40 mA/cm², pH 4.5 and complexing agent concentration of 10 g/L, uniformly distributed, dense and moderately thick Cu-Co alloy plating was obtained, and the weight percentages of Cu and Co reached the peak respectively. The Cu and Co in the waste diamond tools can be recovered under this condition with good recovery effect.

Hollow-Architected Heteroatom-Doped Carbon-Supported Nanoscale Cu/Co as an Enhanced Magnetic Activator for Oxone to Degrade Toxicants in Water.

Even though transition metals can activate Oxone to degrade toxic contaminants, bimetallic materials possess higher catalytic activities because of synergistic effects, making them more attractive for Oxone activation. Herein, nanoscale CuCo-bearing N-doped carbon (CuCoNC) can be designed to afford a hollow structure as well as CuCo species by adopting cobaltic metal organic frameworks as a template. In contrast to Co-bearing N-doped carbon (CoNC), which lacks the Cu dopant, CuCo alloy nanoparticles (NPs) are contained by the Cu dopant within the carbonaceous matrix, giving CuCoNC more prominent electrochemical properties and larger porous structures and highly nitrogen moieties. CuCoNC, as a result, has a significantly higher capability compared to CoNC and Co3O4 NPs, for Oxone activation to degrade a toxic contaminant, Rhodamine B (RDMB). Furthermore, CuCoNC+Oxone has a smaller activation energy for RDMB elimination and maintains its superior effectiveness for removing RDMB in various water conditions. The computational chemistry insights have revealed the RDMB degradation mechanism. This study reveals that CuCoNC is a useful activator for Oxone to eliminate RDMB.

Metastable Phase Formation in Electrodeposited Co-Rich Co-Cu and Co-Ni Alloys

In a previous work [El-Tahawy et al., J. Magn. Magn. Mater. 560, 169660 (2022)], we reported that from a sulfate type bath, hcp-Co can be electrodeposited at high pH and low current density and investigated the structure and magnetoresistance (MR) characteristics of such hcp-Co electrodeposits. Based on this earlier work, Co-rich Co-Cu and Co-Ni alloy electrodeposits were prepared under the same conditions by adding varying amounts of CuSO4 and NiSO4, respectively, to the CoSO4 bath. According to the results of detailed structural studies by various X-ray diffraction (XRD) geometries, in both the Co-Cu and Co-Ni systems an hcp phase formed exclusively up to about 2 at% of the alloying element. Above this concentration, a significant fcc phase fraction appeared in Co-Cu and a minor fcc fraction in Co-Ni up to about 8 at%. This means that the destabilization effect of Cu on hcp-Co is higher than that of Ni. Although the reduction of the stability of hcp-Co with increasing Cu and Ni content is a well-known phenomenon, a quantitative comparison of this effect in Co-Cu and Co-Ni alloys is missing from the literature. The measured lattice constants are analyzed in comparison with Vegard’s law for the Co-Cu and Co-Ni element pairs deduced from data previously reported for the hcp and fcc phases of all three pure elements. For Co-rich Co-Ni alloys, the concentration dependence of the lattice parameters was found to follow Vegard’s law for both the hcp and fcc phases due to the miscibility of the two components. For the Co-rich Co-Cu alloys, the data indicate a positive deviation from Vegard’s law for both the hcp and fcc phases in agreement with the known similar behavior of fcc Co-Cu alloys for the whole composition range. The positive deviation from Vegard’s law in the Co-Cu system is due to the excess mixing volume required for solid solution alloy formation of these immiscible elements in either phases. The MR data are discussed in the light of the observed phases and of the MR parameters reported in our previous work on the hcp and fcc phases of pure Co.

CuCo Nanoparticle, Pd(II), and l-Proline Trifunctionalized UiO-67 Catalyst for Three-Step Sequential Asymmetric Reactions.

Metal-organic frameworks (MOFs) have become a promising support for different active sites to construct multifunctional and heterogeneous catalysts. However, the related investigation mainly focuses on introducing one or two active sites into MOFs and trifunctional catalysts have been very rarely reported. Herein, non-noble CuCo alloy nanoparticles, Pd2+, and l-proline, as encapsulated active species, functional organic linkers, and active metal nodes, respectively, were successfully decorated to UiO-67 to construct a chiral trifunctional catalyst by the one-step method, which was further applied to asymmetric three-step sequential oxidation of aromatic alcohols/Suzuki coupling/asymmetric aldol reactions with excellent oxidation and coupling performance (yields up to 95 and 96%, respectively), as well as good enantioselectivities (eeanti value up to 73%) in asymmetric aldol reactions. The heterogeneous catalyst can be reused at least five times without obvious deactivation due to the strong interaction between the MOFs and the active sites. This work provides an effective strategy to construct multifunctional catalysts via the introduction and combination of three or more of active sites, including encapsulated active species, functional organic linkers, and active metal nodes, into stable MOFs.

Directional assembly of multi-catalytic sites CoCu-MOFs with porous carbon nanofiber templates as efficient catalyst for microbial fuel cells

Designing catalysts with multi catalytic sites is considered as a promising way to solve the sluggish kinetics of the cathodic oxygen reduction reaction (ORR) and improve the performance of electricity generation in microbial fuel cells (MFCs). In this work, a novel hybrid porous electrocatalyst derived from metal-organic frameworks (MOFs) is successfully synthesized, which combines graphene-carbon coated CoCu alloy nanoparticles grown in vertical alignment on carbon nanofibers (CoCu@N-CNFs). Apart from this, CoCu@N-CNFs containing both Co-Nx and Cu-Nx coordination environments enhance oxophilicity, thereby boosting the intrinsic activity of ORR. As expected, CoCu@N-CNFs-1:1 exhibits a superior ORR half-wave potential (−0.545 V vs. Hg/HgCl2) and high limiting current density (10.09 mA cm−2), exceeding that of 20% Pt/C. Furthermore, the MFC equipped with CoCu@N-CNFs-1:1 catalyst achieves maximum power density and coulomb efficiency, which are 102% and 112% higher than Pt/C, respectively. Moreover, CoCu@N-CNFs-1:1 possesses high antibacterial capacity, inhibiting the biofouling on the cathode surface, which further ensures the effective and continuous occurrence of ORR at the triple-phase interface of MFCs.