A robust bifunctional catalyst for rechargeable Zn-air batteries: Ultrathin NiFe-LDH nanowalls vertically anchored on soybean-derived Fe-N-C matrix

ABSTRACT NiFe layered double hydroxide(NiFe-LDH)nanosheets and metal-nitrogen-carbon materials(M-N-C,M=Ni,Fe,Co,etc.)are supreme catalysts in the oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)process,respectively.Nevertheless,the monotonic performance and insufficient stability severely hamper their practical application in rechargeable batteries.Herein,we simultaneously combine ultrathin NiFe-LDH nanowalls with renewable soybean-derived Fe-N-C matrix to obtain a hybrid materials(NiFe-LDH/FeSoy-CNSs-A),which exhibits robust catalytic activities for OER(E_j=10=1.53 V vs.RHE)and ORR(E_1/2=0.91 V vs.RHE),with a top-notch battery parameters and stability in assembled rechargeable Zn-air batteries.Intensive investigations indicate that the vertically dispersed NiFe-LDH nanosheets,Fe-N-C matrix derived from soybean and the strong synergy between them are responsible for the unprecedented OER and ORR performances.The key role of intrinsic N defects involved in the hybrid materials is firstly specified by ultrasoundassisted extraction of soy protein from soybean.The exquisite design can facilitate the utilization of sustainable biomass-derived catalysts,and the mechanism investigations of N defects and oxygenic groups on the structure-activity relationship can stimulate the progress of other functional hybrid electrocatalysts.     

NiCo-LDH nanosheets strongly coupled with GO-CNTs as a hybrid electrocatalyst for oxygen evolution reaction

The rational fabrication of highly efficient electrocatalysts with low cost toward oxygen evolution reaction (OER) is greatly desired but remains a formidable challenge. In this work, we present a facile and straightforward method of incorporating NiCo-layered double hydroxide (NiCo-LDH) into GO-dispersed CNTs (GO-CNTs) with interconnected configuration. X-ray absorption spectroscopy (XAS) reveals the strong electron interaction between NiCo-LDH and the underlying GO-CNTs substrate, which is supposed to facilitate charge transfer and accelerate the kinetics for OER. By tuning the amount of CNTs, the optimized NiCo-LDH/GO-CNTs composite can achieve a low overpotential of 290 mV at 10 mA·cm⁻² current density, a small Tafel slope of 66.8 mV·dec⁻¹ and robust stability, superior to the pure NiCo-LDH and commercial RuO₂ in alkaline media. The preeminent oxygen evolution performance is attributed to the synergistic effect stemming from the merits and the intimate electron interaction between LDH and GO-CNTs. This allows NiCo-LDH/GO-CNTs to be potentially applied in an industrial non-noble metal-based water electrolyzer as the anodic catalysts.

     

Corrosion formation and phase transformation of nickel-iron hydroxide nanosheets array for efficient water oxidation

Designing earth-abundant electrocatalysts with high performance towards water oxidation is highly decisive for the sustainable energy technologies. This study develops a facile natural corrosion approach to fabricate nickel-iron hydroxides for water oxidation. The resulted electrode demonstrates an outstanding activity and stability with an overpotential of 275 mV to deliver 10 mA·cm⁻². Experimental and theoretical results suggest the corrosion-induced formation of hydroxides and their transformation to oxyhydroxides would account for this excellent performance. This work not only provides an interesting corrosion approach for the fabrication of excellent water oxidation electrode, but also bridges traditional corrosion engineering and novel materials fabrication, which would offer some insights in the innovative principles for nanomaterials and energy technologies.

     

Rational design of hierarchically porous Fe-N-doped carbon as efficient electrocatalyst for oxygen reduction reaction and Zn-air batteries

The rational design and construction of hierarchically porous nanostructure for oxygen reduction reaction (ORR) electrocatalysts is crucial to facilitate the exposure of accessible active sites and promote the mass/electron transfer under the gas-solid-liquid triple-phase condition. Herein, an ingenious method through the pyrolysis of creative polyvinylimidazole coordination with Zn/Fe salt precursors is developed to fabricate hierarchically porous Fe-N-doped carbon framework as efficient ORR electrocatalyst. The volatilization of Zn species combined with the nanoscale Kirkendall effect of Fe dopants during the pyrolysis build the hierarchical micro-, meso-, and macroporous nanostructure with a high specific surface area (1,586 m²·g⁻¹), which provide sufficient exposed active sites and multiscale mass/charge transport channels. The optimized electrocatalyst exhibits superior ORR activity and robust stability in both alkaline and acidic electrolytes. The Zn-air battery fabricated by such attractive electrocatalyst as air cathode displays a higher peak power density than that of Pt/C-based Zn-air battery, suggesting the great potential of this electrocatalyst for Zn-air batteries.

     

Spontaneous migration induced Co nanokarstcave encapsulated in N-doped carbon hybrids for efficient oxygen electrocatalyst

Despite the extensive application of porous nanostructures as oxygen electrocatalysts, it is challenging to synthesize single-metal state materials with porous structures, especially the ultrasmall ones due to the uniform diffusion of the same metal. Herein, we pioneer demonstrate a new size effect-based controllable synthesis strategy for the homogeneous Co nanokarstcaves assisted by Co-CN hybrids (CCHs). The preferential migration of cobalt atoms on the surface of small size zeolitic imidazolate framework (ZIF) with high surface energy during pyrolysis is the key factor for the formation of nanokarstcave structure. Furthermore, graphene can act as a diffusion barrier to prevent the agglomeration of nanoparticles in the synthesis process, which also plays an important role in the formation of porous nanostructures. In alkali media, CCHs achieve overpotential of 287 mV (@10 mA·cm⁻²) for oxygen evolution reaction (OER) and a half wave potential of 0.86 V (vs. RHE) for oxygen reduction reaction (ORR).

     

Heterogeneous lamellar-edged Fe-Ni(OH)2/Ni3S2 nanoarray for efficient and stable seawater oxidation

Development of efficient non-precious catalysts for seawater electrolysis is of great significance but challenging due to the sluggish kinetics of oxygen evolution reaction(OER)and the impairment of chlorine electrochemistry at anode.Herein,we report a heterostructure of Ni₃S₂nanoarray with secondary Fe-Ni(OH)₂lamellar edges that exposes abundant active sites towards seawater oxidation.The resultant Fe-Ni(OH)₂/Ni₃S₂nanoarray works directly as a free-standing anodic electrode in alkaline artificial seawater.It only requires an overpotential of 269 mV to afford a current density of 10 mA·cm^-2and the Tafel slope is as low as 46 m V·dec^-1.The 27-hour chronopotentiometry operated at high current density of 100 mA·cm^-2shows negligible deterioration,suggesting good stability of the Fe-Ni(OH)₂/Ni₃S₂@NF electrode.Faraday efficiency for oxygen evolution is up to?95%,revealing decent selectivity of the catalyst in saline water.Such desirable catalytic performance could be benefitted from the introduction of Fe activator and the heterostructure that offers massive active and selective sites.The density functional theory(DFT)calculations indicate that the OER has lower theoretical overpotential than Cl₂ evolution reaction in Fe sites,which is contrary to that of Ni sites.The experimental and theoretical study provides a strong support for the rational design of high-performance Fe-based electrodes for industrial seawater electrolysis.     

Revealing the effect of anion-tuning in bimetallic chalcogenides on electrocatalytic overall water splitting

Enhancing electrocatalytic water splitting performance by modulating the intrinsic electronic structure is of great importance. Here, porous bimetallic oxide and chalcogenide nanosheets grown on carbon paper denoted as NiCo₂X₄/CP (X = O, S, and Se) are prepared to demonstrate how the anion components affect the electronic structures and thereby disclose the correlation between their intermediates interaction and catalytic activities. The experimental characterization and theoretical calculation demonstrate that Se and S substitution can promote the ratio of Co³⁺/Co²⁺ and thereby modulate the electronic structure accompanied with the upshift of d band centers, which not only enhance the inner conductivity but also regulate the interaction between the catalyst surface and intermediates, especially for the adsorption of absorbed H and hydroperoxy intermediates towards respective hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). As a result, a full alkaline electrolyzer using NiCo₂Se₄/CP and NiCo₂S₄/CP as cathode and anode delivers a low voltage of 1.51 V at 10 mA·cm⁻², which is comparable even superior to most transition metal-based electrolyzers.

     

Ultra-stable K metal anode enabled by oxygen-rich carbon cloth

The K metal batteries are emerged as promising alternatives beyond commercialized Li-ion batteries. However, suppressing uncontrolled dendrite is crucial to the accomplishment of K metal batteries. Herein, an oxygen-rich treated carbon cloth (TCC) has been designed as the K plating host to guide K homogeneous nucleation and suppress the dendrite growth. Both density function theory calculations and experimental results demonstrate that abundant oxygen functional groups as K-philic sites on TCC can guide K nucleation and deposition homogeneously. As a result, the TCC electrode exhibits an ultra-long-life over 800 cycles at high current density of 3.0 mA·cm⁻² for 3.0 mA·h·cm⁻². Furthermore, the symmetrical cells can run stably for 2,000 h with low over-potential less than 20 mV at 1.0 mA·cm⁻² for 1.0 mA·h·cm⁻². Even at a higher current of 5.0 mA·cm⁻², the TCC electrode can still stably cycle for 1,400 h.

     

Dandelion-Like Bi2S3/rGO hierarchical microspheres as high-performance anodes for potassium-ion and half/full sodium-ion batteries

Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) have been considered as attractive alternatives for next-generation battery systems, which have promising application potential due to their earth abundance of potassium and sodium, high capacity and suitable working potential, however, the design and application of bi-functional high-performance anode still remain a great challenge up to date. Bismuth sulfide is suitable as anode owing to its unique laminar structure with relatively large interlayer distance to accommodate larger radius ions, high theoretical capacity and high volumetric capacity etc. In this study, dandelion-like Bi₂S₃/rGO hierarchical microspheres as anode material for PIBs displayed reversible capacity, and 206.91 mAh·g⁻¹ could be remained after 1,200 cycles at a current density of 100 mA·g⁻¹. When applied as anode materials for SIBs, 300 mAh·g⁻¹ could be retained after 300 cycles at 2 A·g⁻¹ and its initial Coulombic efficiency is as high as 97.43%. Even at high current density of 10 A·g⁻¹, 120.3 mAh·g⁻¹ could be preserved after 3,400 cycles. The Na₃V₂(PO₄)₃@rGO//Bi₂S₃/rGO sodium ion full cells were successfully assembled which displays stable performance after 60 cycles at 100 mA·g⁻¹. The above results demonstrate that Bi₂S₃/rGO has application potential as high performance bi-functional anode for PIBs and SIBs.

     

Unprecedently low thermal conductivity of unique tellurium nanoribbons

Tellurene, probably one of the most promising two-dimensional (2D) system in the thermoelectric materials, displays ultra-low thermal conductivity. However, a linear thickness-dependent thermal conductivity of unique tellurium nanoribbons in this study reveals that unprecedently low thermal conductivity can be achieved via well-defined nanostructures of low-dimensional tellurium instead of pursuing dimension-reduced 2D tellurene. For thinnest tellurium nanoribbon with thickness of 144 nm, the thermal conductivity is only ∼1.88 ± 0.22 W·m⁻¹·K⁻¹ at room temperature. It’s a dramatic decrease (45%), compared with the well-annealed high-purity bulk tellurium. To be more specific, an expected thermal conductivity of tellurium nanoribbons is even lower than that of 2D tellurene, as a result of strong phonon-surface scattering. We have faith in low-dimensional tellurium in which the thermoelectric performance could realize further breakthrough.

     

Nanovilli electrode boosts hydrogen evolution: A surface with superaerophobicity and superhydrophilicity

Although tremendous efforts have been paid on electrocatalysts toward efficient electrochemical hydrogen generation,breakthrough is still highly needed in the design and synthesis of wonderful non-precious-metal electrocatalyst.Herein,a nanovilli Ni2P electrode,which with superaerophobic and superhydropholic can significantly facilitate the mass and electron transfer was constructed via a facial morphology control strategy.Meanwhile,the substitution of sluggish oxygen evolution with urea oxidation,lowering the two-electrode cell voltage to only 1.48 volts to achieve a current density of 10 mA·cm^-2.Thus,the as-constructed electrode achieves the operation of hydrogen generation by an AA battery.This work sheds new light on the exploration of other high-efficient electrocatalysts for hydrogen generation by using intermittent clean energy.     

Robust enhanced hydrogen production at acidic conditions over molybdenum oxides-stabilized ultrafine palladium electrocatalysts

Electrochemical water splitting is quite seductive for eco-friendly hydrogen fuel energy production,however,the attainment of highly efficient,durable,and cheap catalysts for the hydrogen evolution reaction(HER)remains challenging.In this study,molybdenum oxides stabilized palladium nanoparticle catalysts(MoO_x-Pd)are in situ prepared on commercial carbon cloth(CC)by the facile two-step method of dip-coating and electrochemical reduction.As a self-supported Pd-based catalyst electrode,the MoO_x-Pd/CC presents a competitive Tafel slope of 45.75 mV·dec^-1,an ultralow overpotential of 25 mV,and extremely long cycling durability(one week)in 0.5M H₂S0₄electrolyte,superior to unmodified Pd catalysts and comparable to commercial Pt mesh electrode.On the one hand,the introduction of MoO_xcan inhibit the growth of Pd particles to obtain ultrafine Pd nanoparticles,thus exposing more available active sites.On the other hand,density functional theory(DFT)calculation revealed that MoO_xon the surface of Pd metal can regulate the electronic structure of Pd metal and enhance its intrinsic catalytic activity of HER.This work suggests that transitional metal nanoparticles stabilized by molybdenum oxides are hopeful approaches for obtaining fruitful hydrogen-producing electrocatalysts.     

Single copper sites dispersed on hierarchically porous carbon for improving oxygen reduction reaction towards zinc-air battery

The demand for high-performance non-precious-metal electrocatalysts to replace the noble metal-based catalysts for oxygen reduction reaction(ORR)is intensively increasing.Herein,single-atomic copper sites supported on N-doped three-dimensional hierarchically porous carbon catalyst(Cu₁/NC)was prepared by coordination pyrolysis strategy.Remarkably,the Cu₁/NC-900 catalyst not only exhibits excellent ORR performance with a half-wave potential of 0.894 V(vs.RHE)in alkaline media,outperforming those of commercial Pt/C(0.851 V)and Cu nanoparticles anchored on N-doped porous carbon(CuNPs/NC-900),but also demonstrates high stability and methanol tolerance.Moreover,the Cu₁/NC-900 based Zn-air battery exhibits higher power density,rechargeability and cyclic stability than the one based on Pt/C.Both experimental and theoretical investigations demonstrated that the excellent performance of the as-obtained Cu₁/NC-900 could be attributed to the synergistic effect between copper coordinated by three N atoms active sites and the neighbouring carbon defect,resulting in elevated Cu d-band centers of Cu atoms and facilitating intermediate desorption for ORR process.This study may lead towards the development of highly efficient non-noble metal catalysts for applications in electrochemical energy conversion.     

High power and stable P-doped yolk-shell structured Si@C anode simultaneously enhancing conductivity and Li+ diffusion kinetics

Silicon is a low price and high capacity ancxje material for lithium-ion batteries.The yolk-shell structure can effectively accommodate Si expansion to improve stability.However,the limited rate performance of Si anodes can't meet people's growing demand for high power density.Herein,the phosphorus-doped yolk-shell Si@C materials(P-doped Si@C)were prepared through carbon coating on P-doped Si/SiO_xmatrix to obtain high power and stable devices.Therefore,the as-prepared P-doped Si@C electrodes delivered a rapid increase in Coulombic efficiency from 74.4%to 99.6%after only 6 cycles,high capacity retention of-95%over 800 cycles at 4 A·g^-1,and great rate capability(510 mAh·g^-1at 35 A·g^-1).As a result,P-doped Si@C anodes paired with commercial activated carbon and LiFePO₄cathode to assemble lithium-ion capacitor(high power density of?61,080 W·kg^-1at 20 A·g^-1)and lithium-ion full cell(good rate performance with 68.3 mAh·g^-1at 5 C),respectively.This work can provide an effective way tofurther improve power density and stability for energy storage devices.     

Rapid room-temperature synthesis of a porphyrinic MOF for encapsulating metal nanoparticles

While metal nanoparticles(NPs)have shown great promising applications as heterogeneous catalysts,their agglomeration caused by thermodynamic instability is detrimental to the catalytic performance.To tackle this hurdle,we successfully prepared a functional and stable porphyrinic metal-organic framework(MOF),PCN-224-RT,as a host for encapsulating metal nanoparticles by direct stirring at room temperature.As a result,Pt@PCN-224-RT composites with well-dispersed Pt NPs can be constructed by introducing pre-synthesized Pt NPs into the precursor solution of PCN-224-RT.Of note,the rapid and simple stirring method in this work is more in line with the requirements of environmental friendly and industrialization compared with traditional solvothermal methods.     

Phosphorus-doping activates carbon nanotubes for efficient electroreduction of nitrogen to ammonia

The electrochemical nitrogen reduction reaction (NRR) as an energy-efficient approach for ammonia synthesis is hampered by the low ammonia yield and ambiguous reaction mechanism. Herein, phosphorus-doped carbon nanotube (P-CNTs) is developed as an efficient metal-free electrocatalyst for NRR with a remarkable NH₃ yield of 24.4 μg·h⁻¹·mg⁻¹_cat. and partial current density of 0.61 mA·cm⁻². Such superior activity is found to be from P doping and highly conjugated CNTs substrate. Experimental and theoretical investigations discover that the electron-deficient phosphorus sites with Lewis acidity should be genuine active sites and NRR on P-CNTs follows the distal pathway. These findings provide insightful understanding on NRR processes on P-CNTs, opening up opportunities for the rational design of highly-active cost-effective metal-free catalysts for electrochemical ammonia synthesis.

     

Oxygen-assisted direct growth of large-domain and high-quality graphene on glass targeting advanced optical filter applications

Growing high quality graphene films directly on glass by chemical vapor deposition(CVD)meets a growing demand for constructing high-performance electronic and optoelectronic devices.However,the graphene synthesized by prevailing methodologies is normally of polycrystalline nature with high nucleation density and limited domain size,which significantly handicaps its overall properties and device performances.Herein,we report an oxygen-assisted CVD strategy to allow the direct synthesis of 6-inch-scale graphene glass harvesting markedly increased graphene domain size(from 0.2 to 1.8μm).Significantly,as-produced graphene glass attains record high electrical conductivity(realizing a sheet resistance of 900Ω·sq^-1at a visible-light transmittance of 92%)amongst the state-of-the-art counterparts,readily serving as transparent electrodes for fabricating high-performance optical filter devices.This work might open a new avenue for the scalable production and application of emerging graphene glass materials with high quality and low cost.     

Fast and stable K-ion storage enabled by synergistic interlayer and pore-structure engineering

Carbon-based material has been regarded as one of the most promising electrode materials for potassium-ion batteries (PIBs). However, the battery performance based on reported porous carbon electrodes is still unsatisfactory, while the in-depth K-ion storage mechanism remains relatively ambiguous. Herein, we propose a facile “in situ self-template bubbling” method for synthesizing interlayer-tuned hierarchically porous carbon with different metallic ions, which delivers superior K-ion storage performance, especially the high reversible capacity (360.6 mAh·g⁻¹@0.05 A·g⁻¹), excellent rate capability (158.6 mAh·g⁻¹@10.0 A·g⁻¹) and ultralong high-rate cycling stability (82.8% capacity retention after 2,000 cycles at 5.0 A·g⁻¹). Theoretical simulation reveals the correlations between interlayer distance and K-ion diffusion kinetics. Experimentally, deliberately designed consecutive cyclic voltammetry (CV) measurements, ex situ Raman tests, galvanostatic intermittent titration technique (GITT) method decipher the origin of the excellent rate performance by disentangling the synergistic effect of interlayer and pore-structure engineering. Considering the facile preparation strategy, superior electrochemical performance and insightful mechanism investigations, this work may deepen the fundamental understandings of carbon-based PIBs and related energy storage devices like sodium-ion batteries, aluminum-ion batteries, electrochemical capacitors, and dual-ion batteries.

     

Two-dimensional d-πconjugated metal-organic framework based on hexahydroxytrinaphthylene

The development of new two-dimensional(2D)d-πconjugated metal-organic frameworks(MOFs)holds great promise for the construction of a new generation of porous and semiconductive materials.This paper describes the synthesis,structural characterization,and electronic properties of a new d-πconjugated 2D MOF based on the use of a new ligand 2,3,8,9,14,15-hexahydroxytrinaphthylene.The reticular self-assembly of this largeπ-conjugated organic building block with Cu(II)ions in a mixed solvent system of 1,3-dimethyl-2-imidazolidinone(DMI)and H2 O with the addition of ammonia water or ethylenediamine leads to a highly crystalline MOF Cu3(HHTN)2,which possesses pore aperture of 2.5 nm.Cu3(HHTN)2 MOF shows moderate electrical conductivity of 9.01×10^-8S·cm^-1at 385 K and temperature-dependent band gap ranging from 0.75 to 1.65 eV.After chemical oxidation by l2,the conductivity of Cu3(HHTN)2 can be increased by 360 times.This access to HHTN based MOF adds an important member to previously reported MOF systems with hexagonal lattice,paving the way towards systematic studies of structure-property relationships of semiconductive MOFs.     

Infiltrating lithium into carbon cloth decorated with zinc oxide arrays for dendrite-free lithium metal anode

Lithium metal anode for batteries has attracted extensive attentions, but its application is restricted by the hazardous dendritic Li growth and dead Li formation. To address these issues, a novel Li anode is developed by infiltrating molten Li metal into conductive carbon cloth decorated with zinc oxide arrays. In carbonate-based electrolyte, the symmetric cell shows no short circuit over 1,500 h at 1 mA·cm⁻², and stable voltage profiles at 3 mA·cm⁻² for ∼ 300 h cycling. A low overpotential of ∼ 243 mV over 350 cycles at a high current density of 10 mA·cm⁻² is achieved, compared to the seriously fluctuated voltage and fast short circuit in the cell using bare Li metal. Meanwhile, the asymmetric cell withstands 1,000 cycles at 10 C (1 C = 167 mAh·g⁻¹) compared to the 210 cycles for the cell using bare Li anode. The excellent performance is attributed to the well-regulated Li plating/stripping driven from the formation of LiZn alloy on the wavy carbon fibers, resulting in the suppression of dendrite growth and pulverization of the Li electrode during cycling.