Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Ultrahigh Density of Atomic CoFe-Electron Synergy in Noncontinuous Carbon Matrix for Highly Efficient Magnetic Wave Adsorption

Improving the atom utilization of metals and clarifying the M–M’interaction is both greatly significant in assembling high-performance ultra-light electromagnetic wave-absorbing materials.Herein,a high-temperature explosion strategy has been successfully applied to assemble the hierarchical porous carbon sponge with Co–Fe decoration via the pyrolysis of the energetic metal organic framework.The as-constructed hybrid displays a superior reflection loss(RL)value of-57.7 d B and a specific RL value of-192 d B mg-1 mm-1 at 12.08 GHz with a layer thickness of 2.0 mm(loading of 15 wt%).The off-axis electron hologram characterizes the highly distributed numerous polarized nanodomain variable capacitors,demonstrating the dipole and interfacial polarization along the edges of the nanopores.More importantly,the X-ray absorption spectroscopy analysis verifies the mutual interaction between the metal cluster and carbon matrix and the electronic coupling responsible for the greatly improved electromagnetic wave absorption.

Fullerene-Intercalated Graphitic Carbon Nitride as a HighPerformance Anode Material for Sodium-Ion Batteries

Two-dimensional(2D)graphitic carbon nitride(g-CN)is a promising anode material for sodium-ion batteries(SIBs),but its insufficient interlayer spacing and poor electronic conductivity impede its sodium storage capacity and cycling stability.Herein,we report the fabrication of a fullerene(C_(60))-modified graphitic carbon nitride(C_(60)@CN)material which as an anode material for SIBs shows a high-reversible capacity(430.5 mA h g^(−1) at 0.05 A g^(−1),about 3 times higher than that of pristine g-CN),excellent rate capability(226.6 mA h g^(−1) at 1 A g^(−1))and ultra-long cycle life(101.2 mA h g^(−1) after 5000 cycles at 5 A g^(−1)).Even at a high-active mass loading of 3.7 mg cm^(−2),a reversible capacity of 316.3 mA h g^(−1) can be obtained after 100 cycles.Such outstanding performance of C_(60)@CN is attributed to the C_(60) molecules distributed in the g-CN nanosheets,which enhance the electronic conductivity and prevent g-CN sheets from restacking,thus resulting in enlarged interlayer spacing and exposed edge N defects(pyridinic N and pyrrolic N)for sodium-ion storage.Furthermore,a sodium-ion full cell combining C60@CN anode and NVPF@rGO cathode provides high-coulombic efficiency(>96.5%),exceptionally high-energy density(359.8 W h kganode−1 at power density of 105.1 W kganode−1)and excellent cycling stability(89.2%capacity retention over 500 cycles at 1Aganode−1).This work brings new insights into the field of carbon-based anode materials for SIBs.

Polyoxometalate-Incorporated Host-Guest Framework Derived Layered Double Hydroxide Composites for High-Performance Hybrid Supercapacitor

Metal organic frameworks have been employed as high-performance layered double hydroxide(LDH)composite supercapacitor electrode materials but have shown unsatisfactory redox ability and stability.Herein,a host-guest CuMo-based polyoxomet-alate-based metal organic framework(POMOF)with copious electrochemically active sites and strong electrochemical redox activi-ties has been effectively coupled with POM-incorporated CoNi-LDH to develop a nanocomposite(NENU-5@CoNi-LDH)by a simple solvothermal method.The designed electrode shows a high specific capacity of 333.61 mAh·g^(-1) at 1 A·g^(-1).In addition,the novel hy-brid symmetric supercapacitor NENU-5@CoNi-LDH/active carbon(AC)demonstrated a high energy density of 80.8 Wh·kg^(-1) at a power density of 750.7 W·kg^(-1).Interestingly,the nanocomposite of NENU-5@CoNi-LDH exhibits an outstanding capacitance reten-tion of 79%after 5000 charge-discharge cycles at 10 A·g^(-1).This work provides a new strategy and will be the backbone for future energy storage research.

Co-Ni Electromagnetic Coupling in Hollow Mo_(2)C/NC Sphere for Enhancing Electromagnetic Wave Absorbing Performance

For enhancing the electromagnetic wave(EW)attenuation and adsorption,rational constructing and homogeneously distributing bimetallic electromagnetic coupling units in hollow structure is an effective way,but hard to achieve.Herein,a CoNi-doped hybrid zeolite imidazole framework was synthesized as precursor,which was further converted into a hollow CoNi-bimetallic doped molyb-denum carbide sphere(H-CoNi@MoC/NC)through a two-step etching and calcination strategy.At the loading amount of 15 wt%,a strong absorption of minimum reflection loss(RL_(min))of-60.05 dB at 7.2 GHz with the thickness of 3.1 mm and a wide effective ad-sorption bandwidth(EAB)of 3.52 GHz at the thickness of 2.5 mm were achieved,which was far beyond the reported MoC-based metallic hybrids.The crucial synergistic Co-Ni electromagnetic coupling effect in the composite was characterized,not only enhanc-ing the dipolar/interfacial polarization,but also promoting the impedance matching,displaying the optimized EW absorbing perfor-mance.

Carbon polyhedra encapsulated Si derived from Co-Mo bimetal MOFs as anode materials for lithium-ion batteries

Silicon(Si)holds promise as an anode material for lithium-ion batteries(LIBs)as it is widely avail-able and characterized by high specific capacity and suitable working potential.However,the relatively low electrical conductivity of Si and the significantly high extent of volume expansion realized dur-ing lithiation hinder its practical application.We prepared N-doped carbon polyhedral micro cage en-capsulated Si nanoparticles derived from Co-Mo bimetal metal-organic framework(MOFs)(denoted as Si/CoMo@NCP)and explored their lithium storage performance as anode materials to address these prob-lems.The Si/CoMo@NCP anode exhibited a high reversible lithium storage capacity(1013 mAh g^(−1)at 0.5 A g^(−1)after 100 cycles),stable cycle performance(745 mAh g^(−1)at 1 A g^(−1)after 400 cycles),and excellent rate performance(723 mAh g^(−1)at 2 A g^(−1)).Also,the constructed the full-cell NCM 811//Si/CoMo@NCP exhibited well reversible capacity.The excellent electrochemical performances of Si/CoMo@NCP were at-tributed to two unique properties.The encapsulation of NCP with doped nitrogen and porous structural carbon improves the electrical conductivity and cycling stability of the molecules.The introductions of metallic cobalt and its oxides help to improve the rate capability and lithiation capacity of the materials following multi-electron reaction mechanisms.

Water-soluble copper-based simulated enzyme:Biomimetic synthesis and activities in vitro

Two copper(Ⅱ)complexes were obtained by solvothermal reaction induced by isonicotinic acid ligand through the study of natural simulated enzymes.The activity of superoxide dismutase(SOD)1 and 2 is higher than that of most Cu-SOD mimics,and they have the activity of catechol analogues.It is found that SOD activity and cat-echolase activity are directly affected by the coordination configuration of the central metal atom and the ability of the complex to accept electrons.It is also responsible for the excellent enzyme activity of these two Cu-based complexes.The results of MTT assay show that complexes 1 and 2 have no significant inhibitory effect on cell proliferation.It has good application potential in the clinical biomedical field in the future.

Surface decorated Ni sites for superior photocatalytic hydrogen production

Precise construction of isolated reactive centers on semiconductors with well-controlled configurations affords a great opportunity to investigate the reaction mechanisms in the photocatalytic process and realize the targeted conversion of solar energy to steer the charge kinetics for hydrogen evolution.In the current research,we decorated isolated Ni atoms on the surface of CdS nanowires for efficient photocatalytic hydrogen production.X-ray absorption fine structure investigations clearly demonstrate the atomical dispersion of Ni sites on the surface of CdS nanowires.Experimental investigations reveal that the isolated Ni atoms not only perform well as the real reactive centers but also greatly accelerate the electron transfer via direct Ni-S coordination.Theoretical simulation further documents that the hydrogen adsorption process has also been enhanced over the semi-coordinated Ni centers through electronic coupling at the atomic scale.

Enhanced ionic diffusion interface in hierarchical metal-organic framework@layered double hydroxide for high-performance hybrid supercapacitors

Layered double hydroxides(LDHs)with abundant accessible active sites are promising electrode materials for hybrid supercapacitor(HSC)due to their ultrahigh theoretical capacitances.However,the structural agglomeration of LDH leads to poor rate capability and durability.Herein,we construct a diffusion-controlled interface in hierarchical architecture of metal-organic framework(MOF)HKUST-1@cobalt-nickel LDH(denoted as HKUST-1@CoNiLDH)through an in situ etching/electro-deposition strategy.The rapid charge transfer and ionic diffusion in HKUST-1@CoNiLDH deliver a remarkable specific capacity of 297.23 mAh·g^(−1) at 1 A·g^(−1),superior to mostly reported LDH-based electrodes.More importantly,the as-prepared HKUST-1@CoNiLDH//activated carbon HSC exhibit a high energy density of 39.8 Wh·kg^(−1) at a power density of 799.9 W·kg^(−1) with an outstanding capacitance retention of 90%after 5,000 charge–discharge cycles.The in-depth understanding of the ionic diffusion among the MOF/LDH interfaces will greatly promote the further development of designing and synthesizing high performance energy conversion and storage devices.

Kinetic and thermodynamic control of tetraphenylethene aggregation-induced emission behaviors

Many aggregation-induced emission(AIE)systems exhibit broad and structureless luminescence emission spectra resembling the Gaussian distribution,which is likely due to kinetically locked molecular conformers in the condensed phase.To verify the hypothesis,a series of tetraphenylethene(TPE)derivatives are synthesized and characterized as aqueous nanoparticle suspensions.It is found that the unsubstituted TPE exhibits reduced fluorescence intensity accompanied by a blueshift of the emission maximum,after the temperature of the aqueous suspension is elevated and cooled to room temperature again.For a naphthalimide-substituted TPE compound,thermal treatment of the AIE aqueous suspension results in complete,irreversible aggregation-caused quenching(ACQ)of fluorescence,which can be restored by a redissolving-precipitation process of thermally treated aggregates.The phenomenon is ascribed as a relative population shift of a kinetic AIE(k-AIE)state to a thermodynamic AIE(t-AIE)or ACQ state,evidenced by differential scanning calorimetry,dynamic light scattering,and scanning electron microscopy.The phenomenon may be universal for many other AIE systems and could be explored as stimuli-responsive materials.