Showing papers on "Cobalt published in 2019"

Cobalt in Nitrogen-Doped Graphene as Single-Atom Catalyst for High-Sulfur Content Lithium–Sulfur Batteries

Abstract: Because of their high theoretical energy density and low cost, lithium–sulfur (Li–S) batteries are promising next-generation energy storage devices. The electrochemical performance of Li–S batteries largely depends on the efficient reversible conversion of Li polysulfides to Li2S in discharge and to elemental S during charging. Here, we report on our discovery that monodisperse cobalt atoms embedded in nitrogen-doped graphene (Co–N/G) can trigger the surface-mediated reaction of Li polysulfides. Using a combination of operando X-ray absorption spectroscopy and first-principles calculation, we reveal that the Co–N–C coordination center serves as a bifunctional electrocatalyst to facilitate both the formation and the decomposition of Li2S in discharge and charge processes, respectively. The S@Co–N/G composite, with a high S mass ratio of 90 wt %, can deliver a gravimetric capacity of 1210 mAh g–1, and it exhibits an areal capacity of 5.1 mAh cm–2 with capacity fading rate of 0.029% per cycle over 100 cycles...

Domino electroreduction of CO 2 to methanol on a molecular catalyst

Abstract: Electrochemical carbon dioxide (CO2) reduction can in principle convert carbon emissions to fuels and value-added chemicals, such as hydrocarbons and alcohols, using renewable energy, but the efficiency of the process is limited by its sluggish kinetics1,2. Molecular catalysts have well defined active sites and accurately tailorable structures that allow mechanism-based performance optimization, and transition-metal complexes have been extensively explored in this regard. However, these catalysts generally lack the ability to promote CO2 reduction beyond the two-electron process to generate more valuable products1,3. Here we show that when immobilized on carbon nanotubes, cobalt phthalocyanine—used previously to reduce CO2 to primarily CO—catalyses the six-electron reduction of CO2 to methanol with appreciable activity and selectivity. We find that the conversion, which proceeds via a distinct domino process with CO as an intermediate, generates methanol with a Faradaic efficiency higher than 40 per cent and a partial current density greater than 10 milliamperes per square centimetre at −0.94 volts with respect to the reversible hydrogen electrode in a near-neutral electrolyte. The catalytic activity decreases over time owing to the detrimental reduction of the phthalocyanine ligand, which can be suppressed by appending electron-donating amino substituents to the phthalocyanine ring. The improved molecule-based electrocatalyst converts CO2 to methanol with considerable activity and selectivity and with stable performance over at least 12 hours. Individual cobalt phthalocyanine derivative molecules immobilized on carbon nanotubes effectively catalyse the electroreduction of CO2 to methanol via a domino process with high activity and selectivity and stable performance.

Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution

Abstract: Monitoring atomic and electronic structure changes on active sites under realistic working conditions is crucial for the rational design of efficient electrocatalysts. Identification of the active structure during the alkaline hydrogen evolution reaction (HER), which is critical to industrial water–alkali electrolysers, remains elusive and is a field of intense research. Here, by virtue of operando X-ray absorption spectroscopy on a uniform cobalt single-site catalyst, we report the atomic-level identification of the dynamic structure of catalytically active sites under alkaline HER. Our results reveal the formation of a high-valence HO–Co1–N2 moiety by the binding between isolated Co1–N4 sites with electrolyte hydroxide, and further unravel the preferred water adsorption reaction intermediate H2O–(HO–Co1–N2). Theoretical simulations rationalize this structural evolution and demonstrate that the highly oxidized Co sites are responsible for the catalytic performance. These findings suggest the electrochemical susceptibility of active sites, providing a coordination-engineered strategy for the advance of single-site catalysis. Carbon-based single-atom catalysts usually rely on nitrogen co-doping to stabilize the single metal atoms as metal–N4 moieties. Now, Wei, Yao and colleagues make use of operando techniques to show that under alkaline hydrogen evolution reaction conditions the Co–N4 active site undergoes structural distortion to a HO–Co–N2 configuration.

Generation of Nanoparticle, Atomic-Cluster, and Single-Atom Cobalt Catalysts from Zeolitic Imidazole Frameworks by Spatial Isolation and Their Use in Zinc-Air Batteries

Abstract: The size effect of transition-metal nanoparticles on electrocatalytic performance remains ambiguous especially when decreasing the size to the atomic level. Herein, we report the spatial isolation of cobalt species on the atomic scale, which was achieved by tuning the zinc dopant content in predesigned bimetallic Zn/Co zeolitic imidazole frameworks (ZnCo-ZIFs), and led to the synthesis of nanoparticles, atomic clusters, and single atoms of Co catalysts on N-doped porous carbon. This synthetic strategy allowed an investigation of the size effect on electrochemical behavior from nanometer to Angstrom dimensions. Single-atom Co catalysts showed superior bifunctional ORR/OER activity, durability, and reversibility in Zn-air batteries compared with the other derivatives and noble-metal Pt/C+RuO2 , which was attributed to the high reactivity and stability of isolated single Co atoms. Our findings open up a new avenue to regulate the metal particle size and catalytic performance of MOF derivatives.

An Isolated Zinc–Cobalt Atomic Pair for Highly Active and Durable Oxygen Reduction

Abstract: A competitive complexation strategy has been developed to construct a novel electrocatalyst with Zn-Co atomic pairs coordinated on N doped carbon support (Zn/CoN-C). Such architecture offers enhanced binding ability of O2 , significantly elongates the O-O length (from 1.23 A to 1.42 A), and thus facilitates the cleavage of O-O bond, showing a theoretical overpotential of 0.335 V during ORR process. As a result, the Zn/CoN-C catalyst exhibits outstanding ORR performance in both alkaline and acid conditions with a half-wave potential of 0.861 and 0.796 V respectively. The in situ XANES analysis suggests Co as the active center during the ORR. The assembled zinc-air battery with Zn/CoN-C as cathode catalyst presents a maximum power density of 230 mW cm-2 along with excellent operation durability. The excellent catalytic activity in acid is also verified by H2 /O2 fuel cell tests (peak power density of 705 mW cm-2 ).

Boosting oxygen evolution of single-atomic ruthenium through electronic coupling with cobalt-iron layered double hydroxides

Abstract: Single atom catalyst, which contains isolated metal atoms singly dispersed on supports, has great potential for achieving high activity and selectivity in hetero-catalysis and electrocatalysis. However, the activity and stability of single atoms and their interaction with support still remains a mystery. Here we show a stable single atomic ruthenium catalyst anchoring on the surface of cobalt iron layered double hydroxides, which possesses a strong electronic coupling between ruthenium and layered double hydroxides. With 0.45 wt.% ruthenium loading, the catalyst exhibits outstanding activity with overpotential 198 mV at the current density of 10 mA cm−2 and a small Tafel slope of 39 mV dec−1 for oxygen evolution reaction. By using operando X-ray absorption spectroscopy, it is disclosed that the isolated single atom ruthenium was kept under the oxidation states of 4+ even at high overpotential due to synergetic electron coupling, which endow exceptional electrocatalytic activity and stability simultaneously. While water splitting offers a carbon-neutral means to store energy, water oxidation is sluggish and corrosive over earth-abundant electrocatalysts. Here, authors show single ruthenium atoms over cobalt-iron layered double hydroxides to be effective and stable oxygen evolution electrocatalysts.

Co Nanoislands Rooted on Co-N-C Nanosheets as Efficient Oxygen Electrocatalyst for Zn-Air Batteries.

Abstract: Developing non-precious-metal bifunctional oxygen reduction and evolution reaction (ORR/OER) catalysts is a major task for promoting the reaction efficiency of Zn-air batteries. Co-based catalysts have been regarded as promising ORR and OER catalysts owing to the multivalence characteristic of cobalt element. Herein, the synthesis of Co nanoislands rooted on Co-N-C nanosheets supported by carbon felts (Co/Co-N-C) is reported. Co nanosheets rooted on the carbon felt derived from electrodeposition are applied as the self-template and cobalt source. The synergistic effect of metal Co islands with OER activity and Co-N-C nanosheets with superior ORR performance leads to good bifuctional catalytic performances. Wavelet transform extended X-ray absorption fine spectroscopy and X-ray photoelectron spectroscopy certify the formation of Co (mainly Co0 ) and the Co-N-C (mainly Co2+ and Co3+ ) structure. As the air-cathode, the assembled aqueous Zn-air battery exhibits a small charge-discharge voltage gap (0.82 V@10 mA cm-2 ) and high power density of 132 mW cm-2 , outperforming the commercial Pt/C catalyst. Additionally, the cable flexible rechargeable Zn-air battery exhibits excellent bendable and durability. Density functional theory calculation is combined with operando X-ray absorption spectroscopy to further elucidate the active sites of oxygen reactions at the Co/Co-N-C cathode in Zn-air battery.

Redox-Inert Fe3+ Ions in Octahedral Sites of Co-Fe Spinel Oxides with Enhanced Oxygen Catalytic Activity for Rechargeable Zinc–Air Batteries

Abstract: Bimetallic cobalt-based spinel is sparking much interest, most notably for its excellent bifunctional performance. However, the effect of Fe3+ doping in Co3 O4 spinel remains poorly understood, mainly because the surface state of a catalyst is difficult to characterize. Herein, a bifunctional oxygen electrode composed of spinel Co2 FeO4 /(Co0.72 Fe0.28 )Td (Co1.28 Fe0.72 )Oct O4 nanoparticles grown on N-doped carbon nanotubes (NCNTs) is designed, which exhibits superior performance to state-of-the-art noble metal catalysts. Theoretical calculations and magnetic measurements reveal that the introduction of Fe3+ ions into the Co3 O4 network causes delocalization of the Co 3d electrons and spin-state transition. Fe3+ ions can effectively activate adjacent Co3+ ions under the action of both spin and charge effect, resulting in the enhanced intrinsic oxygen catalytic activity of the hybrid spinel Co2 FeO4 . This work provides not only a promising bifunctional electrode for zinc-air batteries, but also offers a new insight to understand the Co-Fe spinel oxides for oxygen electrocatalysis.

Deep eutectic solvents for cathode recycling of Li-ion batteries

Abstract: As the consumption of lithium-ion batteries (LIBs) for the transportation and consumer electronic sectors continues to grow, so does the pile of battery waste, with no successful recycling model, as exists for the lead–acid battery. Here, we exhibit a method to recycle LIBs using deep eutectic solvents to extract valuable metals from various chemistries, including lithium cobalt (iii) oxide and lithium nickel manganese cobalt oxide. For the metal extraction from lithium cobalt (iii) oxide, leaching efficiencies of ≥90% were obtained for both cobalt and lithium. It was also found that other battery components, such as aluminium foil and polyvinylidene fluoride binder, can be recovered separately. Deep eutectic solvents could provide a green alternative to conventional methods of LIB recycling and reclaiming strategically important metals, which remain crucial to meet the demand of the exponentially increasing LIB production. The ever-increasing applications for Li-ion batteries in markets call for environmentally friendly and energy-efficient recycling technologies. Here the authors report using a deep eutectic solvent to extract valuable components of Li-ion batteries.

Single-atom cobalt array bound to distorted 1T MoS 2 with ensemble effect for hydrogen evolution catalysis

Abstract: The grand challenge in the development of atomically dispersed metallic catalysts is their low metal-atom loading density, uncontrollable localization and ambiguous interactions with supports, posing difficulty in maximizing their catalytic performance. Here, we achieve an interface catalyst consisting of atomic cobalt array covalently bound to distorted 1T MoS2 nanosheets (SA Co-D 1T MoS2). The phase of MoS2 transforming from 2H to D-1T, induced by strain from lattice mismatch and formation of Co-S covalent bond between Co and MoS2 during the assembly, is found to be essential to form the highly active single-atom array catalyst. SA Co-D 1T MoS2 achieves Pt-like activity toward HER and high long-term stability. Active-site blocking experiment together with density functional theory (DFT) calculations reveal that the superior catalytic behaviour is associated with an ensemble effect via the synergy of Co adatom and S of the D-1T MoS2 support by tuning hydrogen binding mode at the interface.

A Cobalt-Iron Double-Atom Catalyst for the Oxygen Evolution Reaction.

Abstract: Single-atom catalysts exhibit well-defined active sites and potentially maximum atomic efficiency. However, they are unsuitable for reactions that benefit from bimetallic promotion such as the oxygen evolution reaction (OER) in an alkaline medium. Here we show that a single-atom Co precatalyst can be in situ transformed into a Co-Fe double-atom catalyst for the OER. This catalyst exhibits one of the highest turnover frequencies among metal oxides. Electrochemical, microscopic, and spectroscopic data, including those from operando X-ray absorption spectroscopy, reveal a dimeric Co-Fe moiety as the active site of the catalyst. This work demonstrates double-atom catalysis as a promising approach for the development of defined and highly active OER catalysts.

Atomic Co/Ni dual sites and Co/Ni alloy nanoparticles in N-doped porous Janus-like carbon frameworks for bifunctional oxygen electrocatalysis

Abstract: Single-atom electrocatalysts have attracted board interest in the recent years as they combine the advantages of heterogeneous and homogeneous electrocatalysts. Nevertheless, single-atom electrocatalysts with single metal component cannot further satisfy the demand of catalytic properties. This work developed atomic Co/Ni dual sites in N-doped porous carbon Janus-like frameworks through epitaxial growth of cobalt based MOFs on nickel complexes. Structural characterization and atomic-scale transmission electron microscopy revealed the homogeneously dispersed active sites of Co-Ni alloy and single Co/Ni atoms. Electrochemical data strongly demonstrated the advantages of integrating Co-MOF and Ni complex with different topological structures to form a Janus-like structure. The resultant catalysts afforded onset potential of 0.93 V and half-wave potential of 0.84 V for oxygen reduction reaction in alkaline media, and 0.86 V and 0.73 V in acid media, which is better than single noble-metal-free catalysts, even close to commercial Pt/C. Besides, the catalysts also exhibited good oxygen evolution reaction performance (a current density of 10 mA cm−2 at a potential of 1.59 V) and overvoltage between ORR and OER is 0.78 V. Density functional theory calculations indicated the high electrocatalytic activities are originated from the synergetic effect of atomic Co/Ni-N-C bonds and microstructure of the prepared materials. This work paves a new avenue for the development of multiatomic electrocatalysts for energy conversion.

Trifunctional Self-Supporting Cobalt-Embedded Carbon Nanotube Films for ORR, OER, and HER Triggered by Solid Diffusion from Bulk Metal.

Abstract: The development of robust and efficient trifunctional catalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen reaction (HER) is central to regenerative metal-air batteries and overall water splitting. It is still a big challenge to achieve an efficient integration of three functions in one freestanding electrode. Herein, a facile and upscalable strategy is demonstrated, to construct cobalt nanoparticle-encapsulated 3D conductive films (Co/CNFs), which were induced by in situ solid diffusion from bulk cobalt metal. Under high-temperature, volatile cobalt species from bulk cobalt foil are trapped by the contacted nitrogen-rich carbons, followed by catalytic growth of interconnected carbon tubes, forming the 3D structured film. This resulting film can be directly preformed as self-supporting and binder-free electrode, which simultaneously facilitates the ORR, OER, and HER with excellent activities and superior stability. Furthermore, such "all-in-one" film also exhibits remarkable performance for Zn-air batteries and overall water splitting, demonstrating its feasibility for practical applications.

Isolated single atom cobalt in Bi 3 O 4 Br atomic layers to trigger efficient CO 2 photoreduction

Abstract: The design of efficient and stable photocatalysts for robust CO2 reduction without sacrifice reagent or extra photosensitizer is still challenging. Herein, a single-atom catalyst of isolated single atom cobalt incorporated into Bi3O4Br atomic layers is successfully prepared. The cobalt single atoms in the Bi3O4Br favors the charge transition, carrier separation, CO2 adsorption and activation. It can lower the CO2 activation energy barrier through stabilizing the COOH* intermediates and tune the rate-limiting step from the formation of adsorbed intermediate COOH* to be CO* desorption. Taking advantage of cobalt single atoms and two-dimensional ultrathin Bi3O4Br atomic layers, the optimized catalyst can perform light-driven CO2 reduction with a selective CO formation rate of 107.1 µmol g−1 h−1, roughly 4 and 32 times higher than that of atomic layer Bi3O4Br and bulk Bi3O4Br, respectively. While the conversion of CO2 to high-value products provides a promising means to remove and utilize atmospheric carbon, few materials can do so without wasteful, sacrificial reagents. Here, authors prepare single-atom Co on Bi3O4Br nanosheets as CO2 reduction catalysts using water and light.

Implanting Atomic Cobalt within Mesoporous Carbon toward Highly Stable Lithium–Sulfur Batteries

Abstract: Lithium-sulfur (Li-S) batteries hold great promise to serve as next-generation energy storage devices. However, the practical performances of Li-S batteries are severely limited by the sulfur cathode regarding its low conductivity, huge volume change, and the polysulfide shuttle effect. The first two issues have been well addressed by introducing mesoporous carbon hosts to the sulfur cathode. Unfortunately, the nonpolar nature of carbon materials renders poor affinity to polar polysulfides, leaving the shuttling issue unaddressed. In this contribution, atomic cobalt is implanted within the skeleton of mesoporous carbon via a supramolecular self-templating strategy, which simultaneously improves the interaction with polysulfides and maintains the mesoporous structure. Moreover, the atomic cobalt dopants serve as active sites to improve the kinetics of the sulfur redox reactions. With the atomic-cobalt-decorated mesoporous carbon host, a high capacity of 1130 mAh gS-1 at 0.5 C and a high stability with a retention of 74.1% after 300 cycles are realized. Implanting atomic metal in mesoporous carbon demonstrates a feasible strategy to endow nanomaterials with targeted functions for Li-S batteries and broad applications.

Hydride Transfer Reactions Catalyzed by Cobalt Complexes.

Abstract: Cobalt has become increasingly attractive in homogeneous catalysis because of its unique characteristics and outstanding catalytic performance in addition to being cheap and earth-abundant. Hydride transfer processes are involved in a broad range of organic transformations that allow the facile preparation of various useful chemicals and synthetic building blocks. These reactions have continuously received great attention both from academia and industry. In this perspective, we review homogeneous cobalt-catalyzed hydride transfer reactions according to the classified reaction types and provide a comprehensive overview of the design, synthesis, and reactivity of cobalt catalysts, their catalytic applications, and reaction mechanisms.

A Phthalocyanine-Based Layered Two-Dimensional Conjugated Metal-Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction.

Abstract: Layered two-dimensional (2D) conjugated metal-organic frameworks (MOFs) represent a family of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures, excellent electrical conductivity, and highly exposed well-defined molecular active sites. Herein, we report a copper phthalocyanine based 2D conjugated MOF with square-planar cobalt bis(dihydroxy) complexes (Co-O4 ) as linkages (PcCu-O8 -Co) and layer-stacked structures prepared via solvothermal synthesis. PcCu-O8 -Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity (E1/2 =0.83 V vs. RHE, n=3.93, and jL =5.3 mA cm-2 ) in alkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro-electrochemistry and theoretical modeling as well as contrast catalytic tests, we identified the cobalt nodes as ORR active sites. Furthermore, when employed as a cathode electrocatalyst for zinc-air batteries, PcCu-O8 -Co delivers a maximum power density of 94 mW cm-2 , outperforming the state-of-the-art Pt/C electrocatalysts (78.3 mW cm-2 ).

Cobalt nanoparticle-embedded nitrogen-doped carbon/carbon nanotube frameworks derived from a metal–organic framework for tri-functional ORR, OER and HER electrocatalysis

Abstract: Developing active and stable electrocatalysts of earth-abundant elements towards the oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) still remains a crucial challenge. Herein, a cobalt-containing metal-organic framework using adenine as a ligand was synthesized and pyrolyzed without any other precursors, forming a cobalt nanoparticle-embedded nitrogen-doped carbon/carbon nanotube framework (Co@N-CNTF). Due to the abundant active sites of homogeneously distributed cobalt nanoparticles within nitrogen-doped graphitic layers, the resultant Co@N-CNTF catalysts exhibit an efficient and stable electrocatalytic performance as a tri-functional catalyst towards the ORR, OER and HER, including a high half-wave potential of 0.81 V vs. RHE for the ORR, and a low overpotential at 10 mA cm -2 for the OER (0.35 V) and HER (0.22 V). As a proof-of-concept, the Co@N-CNTF as an OER/HER bifunctional catalyst for full water splitting affords an alkaline electrolyzer with 10 mA cm -2 under a stable voltage of 1.71 V. Moreover, an integrated unit of a water-splitting electrolyzer using the Co@N-CNTF catalysts, which is powered with a rechargeable Zn-air battery using the Co@N-CNTF as an ORR/OER bifunctional catalyst on air electrodes, can operate under ambient conditions with high cycling stability, demonstrating the viability and efficiency of the self-powered water-splitting system.

Facile synthesis of petal-like NiCo/NiO-CoO/nanoporous carbon composite based on mixed-metallic MOFs and their application for electrocatalytic oxidation of methanol

Abstract: Porous carbon template decorated with mixed transition metals/metal oxides with tunable architecture is becoming increasingly important and attractive as a kind of novel electrode materials. In this way, mixed-metallic metal-organic frameworks (MOFs) provide an opportunity for fabrication of homogeneous mixed metals/metal oxides distribution in the porous carbon frame without any carbon precursor additive. Also, structures, dimensions and electrochemical performance of MOFs can be readily manipulated by simply tuning the metals molar ratio. In this study, we demonstrate the design and fabrication of petal-like NiCo/NiO-CoO metal/metal oxides with a rational composition embedded in 3D ultrathin nanoporous carbon composite)NiCo/NiO-CoO/NPCC(. This nanocomposite is synthesized by a two-steps procedure involving preparation of bimetallic MOFs by partially substituting Ni2+ in the Ni-MOF structure with Co2+ (Ni-Co/BDC [BDC = 1,4-Benzene dicarboxylic acid]) and direct carbonization process in the N2 atmosphere at 900 °C. The prepared nanocomposite was used directly as a non-precious electrocatalyst for methanol oxidation reaction. The results indicated that, in comparison to the monometallic metal/metal oxides distributed in nanoporous carbon composite (Ni/NiO/NPCC and Co/CoO/NPCC), the mixed metals/metal oxides NiCo/NiO-CoO/NPCC exhibits excellent electrochemical performance toward the anodic oxidation of methanol. The unique ultrathin porous petal-like structure with free pores and the enlarged specific surface area provides fast ion/electron transfer, leading to faster kinetics, lower over-potential, and higher electro-catalytic reactivity. Besides their intriguing structural features, the excellent conductivity of carbon frame, as well as a rational composition of two constituents and synergistic effects from cobalt, nickel and their oxides provides favorable catalytic activity for the electro-oxidation of methanol. Therefore, it is believed that this novel multi-component composites demonstrates good electrocatalytic activity and suitable stability towards the methanol oxidation.

Intramolecular electronic coupling in porous iron cobalt (oxy)phosphide nanoboxes enhances the electrocatalytic activity for oxygen evolution

Abstract: Efficient electrocatalysts are of great importance in improving the water splitting efficiency. Herein, we develop a self-templating strategy to construct porous iron cobalt (oxy)phosphide (Fe–Co–P) nanoboxes as promising pre-catalysts for the oxygen evolution reaction in alkaline solution. The constructed Fe–Co–P nanoboxes exhibit excellent electrocatalytic activity and afford a current density of 10 mA cm−2 at a small overpotential of 269 mV. Moreover, the structural evolution of the metal phosphides in the oxygen evolution process has been well monitored. X-ray absorption near-edge structure analyses and computational studies reveal that the structural merits and the effective intramolecular electronic coupling between the Fe and Co atoms via P/O bridges are responsible for the greatly improved electrocatalytic activity.

Nickel, Manganese, and Cobalt Dissolution from Ni-Rich NMC and Their Effects on NMC622-Graphite Cells

Abstract: Transition metal dissolution from the cathode active material and its deposition on the anode causes significant cell aging, studied most intensively for manganese. Owing to their higher specific energy, the current focus is shifting towards nickel-rich layered LiNixMnyCozO2 (NMC, x + y + z = 1) with x > 0.5, so that the effect of Ni dissolution on cell degradation needs to be understood. This study investigates the dissolution of transition metals from a NMC622 cathode and their subsequent deposition on a graphite anode using operando X-ray absorption spectroscopy. We show that in NMC622-graphite cells transition metals dissolve nearly stoichiometrically at potentials > 4.6 V, highlighting the significance of investigating Ni dissolution/deposition. Using NMC622-graphite full-cells with electrolyte containing the bis(trifluoromethane) sulfonimide (TFSI) salts of either Ni, Mn, or Co, we compare the detrimental impact of these metals on cell performance. Using in-situ and ex-situ XRD, we show that the aging mechanism induced by all three metals is the loss of cycleable lithium in the solid electrolyte interface (SEI) of the graphite. This loss is larger in magnitude when Mn is present in the electrolyte compared to Ni and Co, which we ascribe to a higher activity of deposited Mn towards SEI decomposition in comparison to Ni and Co. (C) The Author(s) 2019. Published by ECS.

Cobalt- and nitrogen-codoped porous carbon catalyst made from core–shell type hybrid metal–organic framework (ZIF-L@ZIF-67) and its efficient oxygen reduction reaction (ORR) activity

Abstract: The development of carbon-based oxygen reduction reaction (ORR) catalysts to substitute the expensive and unstable platinum-based ORR catalysts is of great importance for their optimal utilization in energy conversion and storage. Herein, we report the production of highly active carbon-based ORR catalyst from well-designed core–shell type hybrid metal–organic framework (MOF). Cobalt- and nitrogen-codoped porous carbon leaves (Co,N-PCLs) are prepared via a simple one-step pyrolysis of well-designed leaf-shaped core-shell type hybrid MOFs (ZIF-L@ZIF-67, ZIF (zeolitic imidazolate framework) is a subclass of MOF), which contain two different metal ions (Zn2+ in core and Co2+ in shell) and sufficient nitrogen source with a thin flat morphology. The structural and compositional features of resulting Co,N-PCLs are characterized using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and N2 sorption isotherms, and the analyses reveal that they possess the ideal structural and compositional features for ORR, such as numerous carbon nanotubes (CNTs), substantial Co- and N-doping, large surface area, and high pore volume while maintaining the advantageous thin leaf-shape. Owing to such unique structural and compositional features, Co,N-PCLs display much better ORR activity than their counterparts prepared from the parent materials (ZIF-L or ZIF-67). In addition, Co,N-PCL even shows a better electrochemical stability and a better methanol tolerance compared to commercial Pt/C material.

Fabrication of CdS hierarchical multi-cavity hollow particles for efficient visible light CO2 reduction

Abstract: Designing advanced structures for semiconductor photocatalysts is an effective approach to enhance their performance. However, it is not easy to fabricate functional photocatalytic materials with complex nano-architectures. Here we have developed a sequential solution growth, sulfidation and cation-exchange strategy to fabricate CdS hierarchical multi-cavity hollow particles (HMCHPs). This strategy starts with the growth of Zn-based zeolitic imidazolate framework (ZIF-8) onto cobalt glycerate (Co-G) solid spheres. Sulfidation of the obtained Co-G@ZIF-8 composite particles leads to the formation of CoSx@ZnS HMCHPs, which are converted into CdS HMCHPs via a cation-exchange reaction. Owing to the favourable properties of the well-defined hierarchical hollow structure, the CdS HMCHPs exhibit enhanced activity for photocatalytic CO2 reduction compared with other CdS photocatalysts with solid and common hollow structures. The performance of CdS HMCHPs can be further promoted by loading of Au to reach a CO generation rate of 3758 μmol h−1 g−1 under visible light irradiation.

A Comparative Study of Nickel, Cobalt, and Iron Oxyhydroxide Anodes for the Electrochemical Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

Abstract: 2,5-Furandicarboxylic acid (FDCA) has received increasing attention as a near-market platform chemical that can potentially replace terephthalic acid in the production of commercial and high-perfor...

Shifting Oxygen Charge Towards Octahedral Metal: A Way to Promote Water Oxidation on Cobalt Spinel Oxides

Abstract: Cobalt spinel oxides are a class of promising transition metal (TM) oxides for catalyzing oxygen evolution reaction (OER). Their catalytic activity depends on the electronic structure. In a spinel oxide lattice, each oxygen anion is shared amongst its four nearest transition metal cations, of which one is located within the tetrahedral interstices and the remaining three cations are in the octahedral interstices. This work uncovered the influence of oxygen anion charge distribution on the electronic structure of the redox-active building block Co-O. The charge of oxygen anion tends to shift toward the octahedral-occupied Co instead of tetrahedral-occupied Co, which hence produces strong orbital interaction between octahedral Co and O. Thus, the OER activity can be promoted by pushing more Co into the octahedral site or shifting the oxygen charge towards the redox-active metal center in CoO6 octahedra.

Promoting electrocatalytic overall water splitting with nanohybrid of transition metal nitride-oxynitride

Abstract: Excellent Electrochemical water splitting with remarkable durability can provide a solution for the increasing global energy demand. Herein, we report an efficient and stable overall water splitting system; cobalt nitride-vanadium oxynitride nanohybrid, prepared from the polyaniline (PANI) mediated synthetic protocol. This nanohybrid produces significantly higher water oxidation, proton reduction as well as overall water splitting performances compared to the cobalt nitride, vanadium oxynitride or even noble metal catalyst systems. Only 263 mV overpotential is required to reach 10 mA cm−2 current density for oxygen evolution reaction (OER) and 118 mV for the same in case of hydrogen evolution reaction (HER). Finally, the bifunctional nanohybrid has been explored for the alkaline overall water splitting at cell voltage of 1.64 V to attain 10 mA cm−2 current density with long term stability for 100 h. Post-catalytic analyses have revealed the formation of defect rich amorphous CoOx sites leading to high OER activity, whereas crystalline Co(OH)2-Coδ+-N (0

Dispersed Nickel Cobalt Oxyphosphide Nanoparticles Confined in Multichannel Hollow Carbon Fibers for Photocatalytic CO2 Reduction.

Abstract: Materials for high-efficiency photocatalytic CO2 reduction are desirable for solar-to-carbon fuel conversion. Herein, highly dispersed nickel cobalt oxyphosphide nanoparticles (NiCoOP NPs) were confined in multichannel hollow carbon fibers (MHCFs) to construct the NiCoOP-NPs@MHCFs catalysts for efficient CO2 photoreduction. The synthesis involves electrospinning, phosphidation, and carbonization steps and permits facile tuning of chemical composition. In the catalyst, the mixed metal oxyphosphide NPs with ultrasmall size and high dispersion offer abundant catalytically active sites for redox reactions. At the same time, the multichannel hollow carbon matrix with high conductivity and open ends will effectively promote mass/charge transfer, improve CO2 adsorption, and prevent the metal oxyphosphide NPs from aggregation. The optimized hetero-metal oxyphosphide catalyst exhibits considerable activity for photosensitized CO2 reduction, affording a high CO evolution rate of 16.6 μmol h-1 (per 0.1 mg of catalyst).