Hollow cobalt oxide nanoparticles embedded in nitrogen-doped carbon nanosheets as an efficient bifunctional catalyst for Zn–air battery

Rational design of low-cost, highly electrocatalytic activity, and stable bifunctional electrocatalysts for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) has been a great significant for metal–air batteries. Herein, an efficient bifunctional electrocatalyst based on hollow cobalt oxide nanoparticles embedded in nitrogen-doped carbon nanosheets(Co/N-Pg) is fabricated for Zn–air batteries. A lowcost biomass peach gum, consisting of carbon, oxygen, and hydrogen without other heteroatoms, was used as carbon source to form carbon matrix hosting hollow cobalt oxide nanoparticles. Meanwhile, the melamine was applied as nitrogen source and template precursor, which can convert to carbon-based template graphitic carbon nitride by polycondensation process. Owing to the unique structure and synergistic effect between hollow cobalt oxide nanoparticles and Co-N-C species, the proposal Co/N-Pg catalyst displays not only prominent bifunctional electrocatalytic activities for ORR and OER, but also excellent durability. Remarkably, the assembled Zn–air battery with Co/N-Pg air electrode exhibited a low discharge-charge voltage gap(0.81 V at 50 mA cm^-2) and high peak power density(119 mW cm^-2) with long-term cycling stability. This work presents an effective approach for engineering transition metal oxides and nitrogen modified carbon nanosheets to boost the performance of bifunctional electrocatalysts for Zn–air battery.

Interface Engineering of CoS/CoO@N‑Doped Graphene Nanocomposite for High‑Performance Rechargeable Zn–Air Batteries

Low cost and green fabrication of high-performance electrocatalysts with earth-abundant resources for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are crucial for the large-scale application of rechargeable Zn-air batteries(ZABs).In this work,our density functional theory calculations on the electrocatalyst suggest that the rational construction of interfacial structure can induce local charge redistribution,improve the electronic conductivity and enhance the catalyst stability.In order to realize such a structure,we spatially immobilize heterogeneous CoS/CoO nanocrystals onto N-doped graphene to synthesize a bifunctional electrocatalyst(CoS/CoO@NGNs).The optimization of the composition,interfacial structure and conductivity of the electrocatalyst is conducted to achieve bifunctional catalytic activity and deliver outstanding efficiency and stability for both ORR and OER.The aqueous ZAB with the as-prepared CoS/CoO@NGNs cathode displays a high maximum power density of 137.8 mW cm^−2,a specific capacity of 723.9 mAh g^−1 and excellent cycling stability(continuous operating for 100 h)with a high round-trip efficiency.In addition,the assembled quasi-solid-state ZAB also exhibits outstanding mechanical flexibility besides high battery performances,showing great potential for applications in flexible and wearable electronic devices.

Paper-derived cobalt and nitrogen co-doped carbon nanotube@porous carbon as a nonprecious metal electrocatalyst for the oxygen reduction reaction

The oxygen reduction reaction(ORR)is a vitally important process in fuel cells.The development of high‐performance and low‐cost ORR electrocatalysts with outstanding stability is essential for the commercialization of the electrochemical energy technology.Herein,we report a facile synthesis of cobalt(Co)and nitrogen(N)co‐doped carbon nanotube@porous carbon(Co/N/CNT@PC‐800)electrocatalyst through a one‐step pyrolysis of waste paper,dicyandiamide,and cobalt(II)acetylacetonate.The surface of the hierarchical porous carbon supported a large number of carbon nanotubes(CNTs),which were derived from dicyandiamide through the catalysis of Co.The addition of Co resulted in the formation of a hierarchical micro/mesoporous structure,which was beneficial for the exposure of active sites and rapid transportation of ORR‐relevant species(O2,H+,OH?,and H2O).The doped N and Co formed more active sites to enhance the ORR activity of the electrocatalyst.The Co/N/CNT@PC‐800 material exhibited optimal ORR performance with an onset potential of 0.005 V vs.Ag/AgCl and a half‐wave potential of?0.173 V vs.Ag/AgCl.Meanwhile,the electrocatalyst showed an excellent methanol tolerance and a long‐term operational durability than that of Pt/C,as well as a quasi‐four‐electron reaction pathway.The low‐cost and simple synthesis approach makes the Co/N/CNT@PC‐800 a prospective electrocatalyst for the ORR.Furthermore,this work provides an alternative approach for exploring the use of biomass‐derived electrocatalysts for renewable energy applications.

Correction to:Interface Engineering of CoS/CoO@N-Doped Graphene Nanocomposite for High-Performance Rechargeable Zn-Air Batteries

In the original publication,the label text“Pt/C”in Fig.5 should be“Pt/C+IrO_(2)”.In Fig.5d,the X-axis label“Poten-tial(V vs.RHE)”should be replaced with“Specific capacity(mAh g^(−1))”.In Fig.5e,the Y-axis label“Potential(V vs.RHE)”should be replaced with“Voltage(V)”.In Fig.5g,the X-axis label“Time(h)”should be replaced with“Cycle number(n)”.The Y-axis label“ΔE(V vs.RHE)”should be replaced with“Voltage(V)”.The number“1.4”and“1.6”should be replaced with 1.6 and 2.0,respectively.The cor-responding data analysis and conclusions in the manuscript are not affected and thus not to be changed.The correct Fig.5 is provided in this correction.

Engineering Electronic Density and Coordination Environment of Mn–Nx Sites via Zn Cooperation for Quasi-Solid-State Zinc-Air Batteries

Due to the poor Fenton reactivity,single-atom Mn-based materials are generally identified as one of the most promising active catalysts for oxygen reduction reaction(ORR).Regulating the electronic density and coordination environment of atomically dispersed Mn centers is an effective strategy to enhance ORR activity of Mn-based materials.By introducing Zn sites,atomically dispersed Mn centers with multitudes of coordination(including Zn/Mn–Nx and Mn–Nx moieties)can be constructed to form Mn-based ORR catalyst(Zn/Mn-NC)with dual-atom sites.Around Mn–Nx sites,the Zn atoms can effectively modulate the electronic structure and coordination state of Mn centers in Zn/Mn-NC through d–d orbital coupling.The electronic interaction between Zn and Mn sites improves ORR activity,thereby optimizing the oxygen adsorption energy of Mn sites in Zn/Mn-NC and reducing the overall energy barrier.Zn/Mn-NC displays higher ORR half-wave potential than Pt/C(0.89 V vs 0.86 V).The quasi-solid-state zinc-air battery(ZAB)with Zn/Mn-NC as the cathode displayed excellent rechargeability,recyclability,and mechanical robustness.The strategy presented regulates the electronic density and coordination environment of singleatom Mn-based ORR catalysts in quasi-solid-state ZABs.

Advanced heterostructure of Pd nanosheets@Pt nanoparticles boosts methanol electrooxidation

Heterostructures have emerged as elaborate structures to improve catalytic activity owing to their combined surface and distinct inverse interface.However,fabricating advanced nanocatalysts with facetdependent interface remains an unexploited and promising area.Herein,we render the controlled growth of Pt nanoparticles(NPs)on Pd nanosheets(NSs)by regulating the reduction kinetics of Pt^(2+)with solvents.Specifically,the fast reduction kinetic makes the Pt NPs uniformly deposited on the Pd NSs(U-Pd@Pt HS),while the slow reduction kinetic leads to the preferential growth of Pt NPs on the edge of the Pd NSs(E-Pd@Pt HS).Density functional theory calculations demonstrate that Pd(111)-Pt interface in U-Pd@Pt HS induces the electron-deficient status of Pd substrates,triggering the d-band center downshift and amplifying the Pd-Pt intermetallic interaction.The synergy between the electronic effect and interfacial effect facilitates the removal of poisonous intermediates on U-Pd@Pt HS.By virtue of the Pd NSs@Pt NPs interface,the heterostructure achieves exceptional methanol oxidation reaction activity as well as improved durability.This study innovatively proposes heterostructure engineering with facetdependent interfacial modulation,offering instructive guidelines for the rational design of versatile heterocatalysts.

Synthesis of biomorphic hierarchical CeO_2 microtube with enhanced catalytic activity

A biomorphic CeO2microtube with multiple-pore structure was fabricated by using the cotton as biotemplate,throughcerium nitrate solution infiltration and thermal decomposition.Field emission scanning electron microscope(FESEM),powder X-raydiffraction(XRD),transmission electron microscope(TEM),N2adsorption?desorption isotherms,temperature-programmedreduction(TPR)and CO oxidation were used to characterize the samples.The results indicated that the synthesized products werecomposed of crystallites with grain size about9nm and exhibited a fibrous morphology similar to the original template andpossessed a specific surface area(BET)of62.3m2/g.Compared with the conventional CeO2particles,the synthesized materialsshowed a superior catalytic activity for CO oxidation.For the synthesized fibrous CeO2,the CO conversion at320°C was above90%and a100%CO conversion was obtained at410°C.

Characterization and adsorption behaviors of a novel synthesized mesoporous silica coated carbon composite

A novel mesoporous silica coated carbon composite(denoted SEG) with hierarchical pore structure has been successfully prepared in an aqueous solution that contains triblock copolymer template, aluminum chloride, siliceous source and expanded graphite. Textural property and morphology of the SEG composite were characterized by the combination of X-ray diffraction, N_2 adsorption–desorption, scanning electron microscopy,transmission electron microscopy and Fourier transform infrared measurements. Results show that mesoporous silica is steadily and uniformly grown on the surface of the graphite slices and the thickness of the silica layer can be finely tuned according to the silica/C molar ratio in the initial reaction solution. This newly synthesized SEG composite shows greatly increased adsorption capacity to methylene blue than the pristine expanded graphite in the batch tests. Both Langmuir and Frendlich models were further used to evaluate the adsorption isotherms of methylene blue over expanded graphite and SEG samples with different silica contents. Finally, pseudosecond-order model was used to describe the kinetics of methylene blue over expanded graphite and the silica-carbon composites.

Effects of cerium precursors on surface properties of mesoporous CeMnO_x catalysts for toluene combustion

Mesoporous CeMnOx composite oxides catalysts were prepared by surfactant-assisted co-precipitation method and used for the catalytic oxidation of toluene.The effect of different cerium precursors[Ce(NO3)3 and(NH4)2 Ce(NO3)6] on catalyst structure,surface properties and toluene combustion activities of mesoporous CeMnOx catalysts were investigated.The Ce(Ⅲ)MnOx catalyst prepared from Ce(NO3)3 precursor shows higher catalytic activity,with a 90% conversion temperature of 240℃,which is better than the Ce(Ⅳ)MnOx catalyst derived from[(NH4)2 Ce(NO3)6] precursor.On the basis of characterizations,it reveals that abundant surface content of Mn4+,better redox behavior and larger concentration of surface active oxygen species are responsible for the excellent catalytic performance.

Biotemplated fabrication of hierarchical mesoporous CeO_2 derived from diatom and its application for catalytic oxidation of CO

Hierarchically hollow nanostructures have been the focus of numerous studies due to their prominent physicochemical properties that differ significantly from bulk materials and their potential for extensive applications. We present a novel diatom-based scaffold for the synthesis of hierarchically biomorphic CeO2 with special porous structure via incorporating Ce ions into the frustule.Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and nitrogen adsorption-desorption measurements were adopted to characterize the products. Owing to its unique hierarchical structure and periodic meso-macro scale features, the obtained CeO2 exhibits high catalytic activity in CO oxidation. This facile strategy may design a new way towards replicating desired biological structures for metal oxide catalyst in other potential applications.

Novel 3D porous graphene decorated with Co_3O_4/CeO_2 for high performance supercapacitor power cell

Tremendous research efforts have been aimed at ever-increasing worldwide energy demand. For this purpose, the hybrid supercapacitor power cell were prepared composing 3D porous graphene decorated with Co_3O_4-CeO_2 nano-particles herein by using flower stem as biotemplate. The resulting samples were characterized by field emission scanning electron microscopy（FESEM）, transmission electron microscopy（TEM）, Raman spectra, X-ray diffraction spectroscopy（XRD）, nitrogen adsorption and desorption, X-ray photoelectron spectrogram（XPS）, and electrochemical test. The 3D graphene acted as an excellent carrier together with Co_3O_4-CeO_2 nano-particles, boosting the specific capacitance of composite（221 F/g）, which exceeded the theoretical value limit. This facile biotemplate method of research provided an eco-friendly and cut-price route to obtain high-quality graphene and Co_3O_4-CeO_2nano-composites owing to the unique porous structure derived from original template（flower stem）. The finding presented a simple strategy for fabrication of novel energy storage devices.

Fabrication of highly efficient heterostructured Ag-CeO2/g-C3N4 hybrid photocatalyst with enhanced visible-light photocatalytic activity

On the basis of hydrothermal synthesis of Ag-CeO2 microspheres,Ag-CeO2/g-C3N4 composite photocatalyst with heterostructure was prepared by simple solvent evaporation of Ag-CeO2 and g-C3N4.To characterize the composition,structure,morphology and light absorption properties of the as-prepared Ag-CeO2/g-C3N4 composites,XRD,FTIR XPS,SEM,TEM,PL,BET and UV-vis DRS were used,respectively.The as-prepared photocatalyst was subjected to photocatalytic degradation of pollutants,and the prepared composite material has excellent photocatalytic activity for photodegradation of methylene blue(MB).The research shows that the photocatalytic properties of Ag-CeO2/g-C3N4 composites were related to the mass ratio of Ag-CeO2 microspheres and g-C3N4 nanosheets.When the ratio of Ag-CeO2 microspheres:g-C3N4 is 1:5,the composites have the highest photocatalytic activity,which was 9.6 and 3.3 times that of single Ag-CeO2 and g-C3N4,respectively.The improvement of photocatalytic activity is attributed to the heterostructure between the composite materials and the addition of noble metal silver,and the degradation of methylene blue by the visible light irradiation material is greatly improved.Finally,an attempt was made to analyze the principle of photocatalytic degradation of pollutants in prepared materials.

Biogenic synthesis and catalysis of porous CeO_2 hollow microspheres

Porous CeO2 hollow microspheres were successfully prepared through a facile process by using the rape pollen as the biotemplate. Scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, the N2 adsorption and desorption, X-ray diffraction （XRD）, UV-vis diffuse reflectance spectra, and hydrogen temperature-programmed reduction （H2-TPR） were used for their characterization. The results showed that the obtained materials exhibited the same morphology as that of the pollen template, with a diameter of ca. 10 μm, and the surface was evenly covered with a special network-like structutre with mesh size of about 0.3 μm, and the Brunauer-Emmett-Teller （BET） surface area was measured to be 156 m2/g. The detailed property investigation inferred that the product exhibited better photocatalytic activity in acid fuchsine decolorization under daylight because of higher surface area, smaller crystallite size and higher oxygen capacity.

Optimization of methyl orange removal from aqueous solution by response surface methodology using spent tea leaves as adsorbent

The effective disposal of redundant tea waste is crucial to environmental protection and comprehensive utilization of trash resources. In this work, the removal of methyl orange （MO） from aqueous solution using spent tea leaves as the sorbent was investigated in a batch experiment. First, the effects of various parameters such as temperature, adsorption time, dose of spent tea leaves, and initial concentration of MO were investigated. Then, the response surface methodology （RSM）, based on Box- Behnken design, was employed to obtain the optimum adsorption conditions. The optimal conditions could be obtained at an initial concentration of MO of 9.75 mg·L-1, temperature of 35.3℃, contact time of 63.8 min, and an adsorbent dosage 3.90 g· L-1. Under the optimized condi- tions, the maximal removal of MO was 58.2%. The results indicate that spent tea leaves could be used as an effective and economical adsorbent in the removal of MO from aqueous solution.