Energy Barrier Research Articles

Fe based MOF encapsulating triethylenediamine cobalt complex to prepare a FeN3-CoN3 dual-atom catalyst for efficient ORR in Zn-air batteries

Single-atom catalysts show good oxygen reduction reaction (ORR) performance in metal-air battery. However, the symmetric electron distribution results in discontented adsorption energy of ORR intermediates and a lower ORR activity. Herein, Fe-Co dual-atom catalyst with FeN3-CoN3 configuration was prepared by encapsulating nitrogen-rich ion (triethylenediamine cobalt complex, [Co(en)3]3+) in Fe based MOF cage to greatly enhance ORR performance. Due to the confinement effect of the MOF cage, the encapsulated [Co(en)3]3+ is closer to Fe of MOF, thus easily generating FeN3-CoN3 sites. The FeN3-CoN3 sites can break the symmetric electron distribution of single-atom sites, optimizing adsorption energy of oxygen intermediate. Thus, FeCo-NC exhibits extraordinary ORR activity with a high half-wave potential of 0.915 V and 0.789 V in alkaline and acidic electrolyte, respectively, while it was 0.874 V and 0.79 V for Pt/C. The liquid and solid Zn-air batteries with FeCo-NC as cathode show higher peak power density and specific capacity. DFT results indicate that FeN3-CoN3 site can reduce the reaction energy barrier of the rate-determining step resulting in an excellent ORR performance.

Expediting *OH accumulation kinetics on metal-organic frameworks-derived CoOOH with CeO2 “accelerator” for electrocatalytic 5-hydroxymethylfurfural oxidation valorization

In this work, nickel foam supported CeO2-modified CoBDC (BDC stands for terephthalic acid linker) metal-organic frameworks (NF/CoBDC@CeO2) are prepared by hydrothermal and subsequent impregnation methods, which can be further transformed to NF/CoOOH@CeO2 by reconstruction during the electrocatalytic test. The obtained NF/CoOOH@CeO2 exhibits excellent performance in electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) because the introduction of CeO2 can optimize the electronic structure of the heterointerface and accelerate the accumulation of *OH. It requires only a potential of 1.290 VRHE to provide a current density of 50 mA cm−2 in 1.0 M KOH + 50 mM HMF, which is 222 mV lower than that required in 1.0 M KOH (1.512 VRHE). In addition, density-functional theory calculation results demonstrate that CeO2 biases the electrons to the CoOOH side at the heterointerface and promotes the adsorption of *OH and *HMF on the catalyst surface, which lower the reaction energy barrier and facilitate the electrocatalytic oxidation process.

Highly Performing Sodium Metal Batteries Reinforced by a Self-Regulated Dual-Layered Solid Electrolyte Interphase via a Metal-Organic Framework.

Sodium-metal batteries, heralded for high energy density and cost-effectiveness, are compromised by an unstable solid electrolyte interphase (SEI) and dendrite formation, which hinder practical applications. Herein, a zirconium-based metal-organic framework nanostructure coating (ZMOF-NSC) was constructed in a low-loss, flexible manner. Comprehensive studies show that ZMOF-NSC, with its periodically ordered nanochannels and organized pore structures, enhances ion transport and decreases the Na+ migration energy barrier, thus ensuring uniform ion flux and achieving uniform spherical deposition. Additionally, ZMOF-NSC facilitates partial desolvation, catalyzing the formation of an inorganic-rich, dual-layered SEI that effectively protects the anode and suppresses dendrite formation. Consequently, the ZMOF-NSC@Na symmetric battery exhibits an impressive lifespan of over 2500 h, demonstrating extended operational longevity. The Na3V2(PO4)3∥ZMOF-NSC@Na batteries demonstrate exceptional cycling stability with 81% capacity retention after 2000 cycles at 10 C, maintaining stability over 3000 cycles at 20 C. Moreover, the NVP∥ZMOF-NSC@Na battery achieves an energy density of 370 Wh kg-1 and a power density of 10,484 W kg-1, indicating superior durability and performance. This significant finding highlights the significant potential of structured MOFs to induce a dual-layered SEI, advancing the commercialization of durable, dendrite-free sodium metal batteries. The precise design of self-assembled pore structures and surface active sites in MOFs demonstrates significant potential in advancing the commercialization of durable, dendrite-free electrodes of metal-based rechargeable batteries.

An investigation into transition states of cyclic tetra-atomic silicon and germanium interstellar dust compounds: SixC4-x, GexC4-x, and GexSi4-x (x ∈ {1,2,3}).

Presented in this work is a thorough determination of the transition states between the different isomers of cyclic tetra-atomic silicon carbide, germanium carbide, and germanium silicide clusters. Through use of density functional theory (B3LYP-D3BJ, M06-2X, ωB97X-D4, and B2GP-PLYP) in conjunction with the aug-cc-pVTZ basis set, transition state structures and their barrier heights are determined for the interconversions between the various isomers for the family of tetra-atomic SiC, GeC, and GeSi compounds. SiC dust grains are known to be prevalent in interstellar dust, and among this group, so far only diamond-shaped (d-)SiC3 has been detected in the interstellar medium (ISM). Determining which other structures might be detectable not only depends on their intrinsic spectroscopic features, but whether or not they are likely to exist as isomers in interstellar environments. By examining the energy barrier heights for transitions between isomers, we determined that many of these structures are unlikely to exhibit interconversion in the ISM, outside of hotter circumstellar environments. Although Boltzmann population ratios at approximate circumstellar temperatures suggest the presence of higher energy minima, it is likely that once interconversion happens, as molecules travel away from a star and cool, they will get kinetically trapped in the potential energy well they inhabit, making how the ratios freeze out dependent on the time and pathways the molecules take to cool down. As such, many of these higher energy minima may still be good candidates for detection including (rhomboidal) r-SiC3, r-GeC3, r-GeSi3, (trapezoidal) t-Si2C2, r-Ge2C2, and d-Si3C.

Highly selective regulation of non-radical and radical mechanisms by Co cubic assembly catalysts for peroxymonosulfate activation

Peroxymonosulfate (PMS) activation on efficient catalysts is a promising strategy to produce sulfate radical (SO4−) and singlet oxygen (1O2) for the degradation of refractory organic pollutants. It is a great challenge to selectively generate these two reactive oxygen species, and the regulation mechanism from non-radical to radical pathway and vice versa is not well established. Here, we report a strategy to regulate the activation mechanism of PMS for the selective generation of SO4− and 1O2 with 100 % efficiency by sulfur-doped cobalt cubic assembly catalysts that was derived from the Co-Co Prussian blue analog precursor. This catalyst showed superior catalytic performance in activating PMS with normalized reaction rate increased by 87 times that of the commercial Co3O4 nanoparticles and had much lower activation energy barrier for the degradation of organic pollutant (e.g., p-chlorophenol) (18.32 kJ⋅mol−1). Experimental and theoretical calculation results revealed that S doping can regulate the electronic structure of Co active centers, which alters the direction of electron transfer between catalyst and PMS. This catalyst showed a strong tolerance to common organic compounds and anions in water, wide environmental applicability, and performed well in different real-water systems. This study provides new opportunities for the development of metal catalyst with metal-organic frameworks structure and good self-regeneration ability geared specifically towards PMS-based advanced oxidation processes applied for water remediation.

Room-temperature hydrogen adsorption in Pd nanoparticle decorated UiO-66-NH2 via spillover

To improve room-temperature hydrogen storage, palladium (Pd) nanoparticles were innovatively decorated by carbon bridge onto the amino-group functioned Zr-terephthalate metal-organic framework (MOF) UiO-66 to reduce the diffusion energy barrier and then improve the hydrogen spillover effect. Powder X-ray diffraction shows broad Pd peak and retained UiO-66-NH2 integrity after Pd decoration. The hydrogen uptake capacity show that UiO-66-NH2-Pd exhibits best hydrogen storage performance than UiO-66-NH2 and pristine UiO-66. The hydrogen up taken in Pd decorated UiO-66 (UiO-66-NH2-1Pd) was close to 4 wt.% under 20 MPa at room temperature. Density functional theory (DFT) calculations show that hydrogen adsorption energy of UiO-66-NH2-Pd was –0.5897 eV, which was much lower than that of UiO-66-NH2 (–0.3716 eV) and UiO-66 (–0.2975 eV). Ultimately, Pd decorated NH2 group functioned UiO-66 enable improve storage capacities through hydrogen spillover under ambient conditions which could satisfy the demand for sustainable energy, especially for the long-term storage energy media.

Influence of cutoff radius and tip atomic structure on energy barriers encountered during AFM tip sliding on 2D monolayers

In computational studies using the Lennard–Jones (LJ) potential, the widely adopted 2.5 σ cutoff radius effectively truncates pairwise interactions across diverse systems (Santra et al 2008 J. Chem. Phys. 129 234704, Chen and Gao 2021 Friction 9 502–12, Bolintineanu et al 2014 Part. Mech. 1 321–56, Takahiro and Kazuhiro 2010 J. Phys.: Conf. Ser. 215 012123, Zhou et al 2016 Fuel 180 718–26, Toxvaerd and Dyre 2011 J. Chem. Phys. 134 081102, Toxvaerd and Dyre 2011 J. Chem. Phys. 134 081102). Here, we assess its adequacy in determining energy barriers encountered by a Si monoatomic tip sliding on various two-dimensional (2D) monolayers, which is crucial for understanding nanoscale friction. Our findings emphasize the necessity of a cutoff radius of at least 3.5 σ to achieve energy barrier values exceeding 95% accuracy across all studied 2D monolayers. Specifically, 3.5 σ corresponds to 12.70 Å in graphene, 12.99 Å in MoS2 and 13.25 Å in MoSe2. The barrier values calculated using this cutoff support previous experiments comparing friction between different orientations of graphene and between graphene and MoS2 (Almeida et al 2016 Sci. Rep. 6 31569, Zhang et al 2014 Sci. China 57 663–7). Furthermore, we demonstrate the applicability of the 3.5 σ cutoff for graphene on an Au substrate and bilayer graphene. Additionally, we investigate how the atomic configuration of the tip influences the energy barrier, finding a nearly threefold increase in the barrier along the zigzag direction of graphene when using a Si(001) tip composed of seven Si atoms compared to a monoatomic Si tip.

Investigation of numerical transport models in protein-based molecular junctions with cofactors of diverse chemical natures

The cofactors of proteins dictate the charge transport mechanism across molecular junctions when self-assembled protein monolayers are sandwiched between two metal electrodes. Here, we summarized how the chemical coordination nature of cofactors in various proteins modulates electrical conductance by investigating electronic transport studies across different protein-based molecular junctions under various forces applied under the AFM tip. We have utilized several numerical techniques of electronic transport to analyse the experimentally obtained current–voltage measurements across various protein-based molecular junctions and depicted the origin of electronic modulation in the electrical conductance under different external stimuli. We could also find the origin of electronic conductance modulation under external stimuli at various applied forces by obtaining several analytical transport parameters such as energy barrier, coupling strength, and electrical conductance values. Utilizing density-functional-theory calculations, we further validate that the electronic density of states present in the cofactors within the proteins dominates the electronic transport behaviours across protein-based molecular junctions. Our findings reveal the limiting factor for applying various external stimuli on different proteins, which could be further valuable in bioelectronic applications. We have also found that the organic cofactor containing protein follows all the tunneling mechanism-related numerical transport models and the electronic transport across proteins with pure inorganic cofactors follows Landauer transport formalism.

Curvature-induced enhancement of thermal stability of skyrmions

Geometry plays an important role in the nucleation, stabilization, and manipulation of magnetization patterns within magnetic nanoelements. This work analyzes the impact of curvature on the thermal stability of skyrmions hosted on Gaussian-shaped nanoshells. Based on annihilation processes observed in flat nanoparticles, three distinct annihilation processes—skyrmion contraction, expansion, and displacement toward the nanodot border—are analyzed. We show that curvature-induced effective interactions significantly alter the energy barriers associated with these annihilation processes. The changes in energy are related to the relative alignment between the skyrmion core and the direction normal to the surface, highlighting the presence of favorable and unfavorable chiralities for skyrmion stabilization in curved nanodots. We also show that, unlike the one obtained for flat nanodots, where the skyrmion lifetimes typically span seconds, the lowest energy barrier values in curved nanodots reach values that ensure skyrmion lifetimes at room temperature to months before thermal fluctuations annihilate them. Curvature parameters can control the annihilation mechanism. This enhancement in skyrmion stability holds even without external additional stimuli. This underscores the profound impact of curvature on the dynamic behavior and thermal stability of skyrmions within magnetic nanoelements.

A-Site Cations Impact on Nonradiative Recombination, Mobility, and Defect Dynamics in Sn-Based Perovskites.

Sn-based perovskites with different cations in the A-site exhibit distinct electronic structures and dynamic properties. By utilizing time-dependent density functional theory and nonadiabatic molecular dynamics, we demonstrate that larger FA cations decrease wave function overlap between initial and final states and slow down nuclear motion. In the case of FASnI3, this alteration decreases the nonadiabatic coupling and increases the nonradiative electron-hole recombination time by 130% and 76%, respectively, compared to CsSnI3 and MASnI3 (CH3NH3SnI3). Furthermore, A-site modification significantly improves electron mobility and changes the properties of defects in FASnI3 (HC(NH2)2SnI3), which achieves higher electron mobility through a polar optical phonon-dominated scattering mechanism and exhibits higher defect formation energy and migration barriers of A-site cations due to increased steric hindrance, relative to CsSnI3 and MASnI3. These results emphasize the critical function of A-site cation substitution in controlling nonradiative recombination dynamics, electron mobility, and defect characteristics in Sn-based perovskites and provide theoretical insights for the advancement of novel lead-free perovskite materials.

MOF-on-MOF Heterostructured Electrocatalysts for Efficient Nitrate Reduction to Ammonia.

Electrocatalytic nitrate reduction reaction (NO3-RR) is an important route for sustainable NH3 synthesis and environmental remediation. Metal-organic frameworks (MOFs) are one family of promising NO3-RR electrocatalysts, however,there is plenty of room to improve in their performance, calling for new design principles. Herein, a MOF-on-MOF heterostructured electrocatalyst with interfacial dual active sites and build-in electric field is fabricated for efficient NO3-RR to NH3 production. By growing Co-HHTP (HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) nanorods on Ni-BDC (BDC=1,4-benzenedicarboxylate) nanosheets, experimental and theoretical investigations demonstrate the formation of Ni-O-Co bonds at the interface of MOF-on-MOF heterostructure, leading to dual active sites tailed for NO3-RR. The Ni sites facilitate the adsorption and activation of NO3-, while the Co sites boost the H2O decomposition to supply active hydrogen (Hads) for N-containing intermediates hydrogenation on adjacent Ni sites, cooperatively reducing the energy barriers of NO3-RR process. Together with the accelerated electron transfer enabled by built-in electric field, remarkable NO3-RR performance is achieved with an NH3 yield rate of 11.46mg h-1cm-2 and a Faradaic efficiency of 98.4%, outperforming most reported MOF-based electrocatalysts. This work provides new insights into the design of high-performance NO3-RR electrocatalysts.

Maximizing CO2 reduction efficiency: surface‐regulated highly porous Ag‐Cu alloy aerogel inserted with multi‐wall carbon nanotube achieving nearly complete CO selectivity

The electrochemical reduction of CO2 (eCO2RR) holds promise in mitigating atmospheric greenhouse gas levels but is hindered by low reaction kinetics, high energy barriers, and poor selectivity. To address these challenges, we developed a novel series of cost‐effective AgCu‐containing metal‐aerogel catalysts with high electrochemical surface areas (ECSA) using a top‐down reduction approach. The Ag85Cu15 aerogel, with an ECSA of 27.41 cm², achieved a Faraday efficiency (FE%) of 89.3% for CO production at ‐0.9 V vs. RHE. Increasing the Cu content to over 50% in the aerogel matrix produced small amounts of C2H4, with a maximum FE% of 12.9% at ‐1.0 V vs. RHE. To further enhance CO2 reduction efficiency, multi‐walled carbon nanotubes (CNT) were incorporated into the Ag85Cu15 alloy aerogel via a hydrothermal treatment. The highly dispersed CNTs within the aerogel matrix increased the ECSA to 57.00 cm² by forming a well‐defined porous structure through van‐der Waals interactions, improving CO selectivity, and achieving a FE% of 98.6% at ‐0.7 V vs. RHE and a partial current density of 9.6 mA/cm² in an H‐cell. 86% of the initial FECO% was maintained during an 18 h test with continuous electrolysis.

Hypervalent Chalcogen Bonds Catalysis on the Intramolecular Aza-Michael Reaction of Aminochalcone: Catalytic Performance and Chalcogen Bond Properties.

Chalcogen bond (ChB) catalysis, as a new type in the field of non-covalent bond catalysis, has become a hot research topic in the field of organocatalysis in recent years. In the present work, we investigated the catalytic performance of a series of hypervalent ChB catalysis based on the intramolecular Aza-Michael reaction of aminochalcone. The reaction includes the carbon-nitrogen bond coupling step (key step) and the proton transfer step. The catalytic performance of mono-dentate pentafluorophenyl chalcogen bond donor ChB1 was comparable to that of bis-dentate chalcogen bond donor ChB4, and stronger than that of mono-dentate chalcogen bond donors ChB2 and ChB3. The formation of the chalcogen bond between the catalyst and the carbonyl oxygen atom of the reactant, causing the charge rearrangement of the reactant and C(1) charge of the -C-Ph group to become more positive, thereby the ChB catalysis promoted the nucleophile reaction. The electron density of the chalcogen bond of the pre-complex, the most positive electrostatic potentials of the catalyst, and the NPA charge of the key atom are proportional to the Gibbs energy barrier of the C-N bond coupling process, which provides an idea to predict the catalytic activity of the ChB catalysis.

Programmed Heterostructures for Enhanced Electrical Conductivity.

Interfacial electron transport in multicomponent systems plays a crucial role in controlling electrical conductivity. Organic-inorganic heterostructures electronic devices where all the entities are covalently bonded to each other can reduce interfacial electrical resistance, thus suitable for low-power consumption electronic operations. Programmed heterostructures of covalently bonded interfaces between ITO-ethynylbenzene (EB) and EB-zinc ferrite (ZF) nanoparticles, a programmed structure showing 67 978-fold enhancement of electrical current as compared to pristine NPs-based two terminal devices are created. An electrochemical approach is adopted to prepare nearly π-conjugated EB oligomer films of thickness ≈26nm on ITO-electrode on which ZF NPs are chemically attached. A "flip-chip" method is employed to combine two EB-ZnFe2O4 NPs-ITO to probe electrical conductivity and charge conduction mechanism. The EB-ZnFe2O4 NPs exhibit strong electronic coupling at ITO-EB and EB-NPs with an energy barrier of 0.13eV between the ITO Fermi level and the LUMO of EB-ZF NPs for efficient charge transport. Both the DC and AC-based electrical measurements manifest a low resistance at ITO-EB and EB-ZF NPs, revealing enhanced electrical current at ± 1.5V. The programmed heterostructure devices can meet a strategy to create well-controlled molecular layers for electronic applications toward miniaturized components that shorten charge carrier distance, and interfacial resistance.

Theoretical Investigation on Water-Free, Water- and Self-Assisted H-Abstraction Reactions from Dimethylamine by Hydroxy Radicals.

Accurate branching ratios of the H-abstraction reactions from dimethylamine (DMA) by OH radicals are important in understanding the atmospheric fate of DMA. In this work, the reaction kinetics of the water-free, water-assisted, and self-assisted H-abstraction reactions between DMA and OH radicals are accurately determined using the multipath canonical variational theory with the small-curvature tunneling correction, to explore the catalytic effects of the reactant (DMA) and product (water). To choose a suitable method that well describes the current reaction systems, various combinations with seven DFT methods and six basis sets are first evaluated, and the M08-HX/ma-TZVP method is identified as the most appropriate, with a mean unsigned deviation of 0.9 kcal mol-1 against the gold-standard CCSD(T)/CBS(T-Q) method. Based on the determined potential energy surfaces with the considerations of ground-state structures and specific-reaction parameters of zero-point energies, rate constants and branching ratios are calculated in a wide temperature range. The calculations show that the participation of water and DMA can lead to three-body complexes with a lower energy and influence the energy barriers, but neither of them shows the catalytic effect on the H-abstraction reactions in terms of kinetics. Additionally, the branching ratio analysis demonstrates that the product distribution is significantly altered in the presence of DMA and water.

Utilizing cost-effective pyrocarbon for highly efficient gold retrieval from e-waste leachate

Addressing burdens of electronic waste (E-waste) leachate while achieving sustainable and selective recovery of noble metals, such as gold, is highly demanded due to its limited supply and escalating prices. Here we demonstrate an environmentally-benign and practical approach for gold recovery from E-waste leachate using alginate-derived pyrocarbon sorbent. The sorbent demonstrates potent gold recovery performance compared to most previously reported advanced sorbents, showcasing high recovery capacity of 2829.7 mg g−1, high efficiency (>99.5%), remarkable selectivity (Kd ~ 3.1 × 108 mL g−1), and robust anti-interference capabilities within environmentally relevant contexts. The aromatic structures of pyrocarbon serve as crucial electrons sources, enabling a hydroxylation process that simultaneously generates electrons and phenolic hydroxyls for the reduction of gold ions. Our investigations further uncover a “stepwise” nucleation mechanism, in which gold ions are reduced as intermediate gold-chlorine clusters, facilitating rapid reduction process by lowering energy barriers from 1.08 to −21.84 eV. Technoeconomic analysis demonstrates its economic viability with an input-output ratio as high as 1370%. Our protocol obviates the necessity for organic reagents whilst obtaining 23.96 karats gold product from real-world central processing units (CPUs) leachates. This work introduces a green sorption technique for gold recovery, emphasizing its role in promoting a circular economy and environmental sustainability.

High-purity ethylene production via indirect carbon dioxide electrochemical reduction

High-purity ethylene production from CO2 electroreduction (CO2RR) is a coveted, yet arduous feat because the product stream comprises a blend of unreacted CO2, H2, and other off-target CO2 reduction products. Here we present an indirect reduction strategy for CO2-to-ethylene conversion, one that employs 2-bromoethanol (Br-EO) as a mediator. Br-EO is initially generated from CO2RR and subsequently undergoes reduction to ethylene without the need for energy-intensive separation steps. The optimized AC-Ag/C catalyst with Cl incorporation reduces the energy barrier of the debromination step during Br-EO reduction, and accelerates the mass-transfer process, delivering a 4-fold decrease of the relaxation time constant. Resultantly, AC-Ag/C achieved a FEethylene of over 95.0 ± 0.36% at a low potential of −0.08 V versus reversible hydrogen electrode (RHE) in an H-type cell with 0.5 M KCl electrolyte, alongside a near 100% selectivity within the range of −0.38 to −0.58 V versus RHE. Through this indirect strategy, the average ethylene purity within 6-hour electrolysis was 98.00 ± 1.45 wt%, at −0.48 V (vs RHE) from the neutralized electrolyte after CO2 reduction over the Cu/Cu2O catalyst in a flow-cell.

Electrosynthesis of Ammonia from Nitrate Using a Self-Activated Carbon Fiber Paper.

While electrochemically upcycling nitrate wastes to valuable ammonia is considered a very promising pathway for tackling the environmental and energy challenges underlying the nitrogen cycle, the effective catalysts involved are mainly limited to metal-based materials. Here, we report that commercial carbon fiber paper, which is a classical current collector and is typically assumed to be electrochemically inert, can be significantly activated during the reaction. As a result, it shows a high NH3 Faradaic efficiency of 87.39% at an industrial-level current density of 300 mA cm-2 for over 90 h of continuous operation, with a NH3 production rate of as high as 1.22 mmol cm-2 h-1. Through experimental and theoretical analysis, the in situ-formed oxygen functional groups are demonstrated to be responsible for the NO3RR performance. Among them, the C-O-C group is finally identified as the active center, which lowers the thermodynamic energy barrier and simultaneously improves the hydrogenation kinetics. Moreover, high-purity NH4Cl and NH3·H2O were obtained by coupling the NO3RR with an air-stripping approach, providing an effective way for converting nitrate waste into high-value-added NH3 products.

Plasmon-Driven Highly Selective CO2 Photoreduction to C2H4 on Ionic Liquid-Mediated Copper Nanowires.

Selective CO2 photoreduction to value-added multi-carbon (C2+) feedstocks, such as C2H4, holds great promise in direct solar-to-chemical conversion for a carbon-neutral future. Nevertheless, the performance is largely inhibited by the high energy barrier of C-C coupling process, thereby leading to C2+ products with low selectivity. Here we report that through facile surface immobilization of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) ionic liquid, plasmonic Cu nanowires could enable highly selective CO2 photoreduction to C2H4 product. At an optimal condition, the resultant plasmonic photocatalyst exhibits C2H4 production with selectivity up to 96.7% under 450 nm monochromatic light irradiation, greatly surpassing its pristine Cu counterpart. Combined in situ spectroscopies and computational calculations unravel that the addition of EMIM-BF4 ionic liquid modulates the local electronic structure of Cu, resulting in its enhanced adsorption strength of *CO intermediate and significantly reduced energy barrier of C-C coupling process. This work paves new path for Cu surface plasmons in selective artificial photosynthesis to targeted products.

Interface engineering assisted La1-xSrxCoO3/FeOOH heterostructure as a high-performance electrocatalyst for oxygen evolution reaction

Perovskite oxides play a crucial role as catalysts in the oxygen evolution reaction (OER) owing to their distinctive structure and diverse physical and chemical characteristics. Currently, enhancing the electronic structure and specific surface area of the perovskite surface through strategic regulation poses a significant challenge in the advancement of perovskite catalyst development. Here, we propose a novel method for enhancing the OER activity of LaCoO3 (LCO) perovskite through atomic doping and interface engineering. The La0.6Sr0.4CoO3–FeOOH (Fe-LSCO) composite exhibits a notable enhancement in electrocatalytic performance, manifesting a low overpotential of 296.3 mV for the oxygen evolution reaction (OER) at a current density of 10 mA cm−2, while maintaining a high level of activity for a duration of 120 h. The enhanced activity of Fe-LSCO can be attributed to oxygen vacancy defects and the increase of the active site caused by A-site-doping and amorphous nanosheets of FeOOH, which synergistic effect reduces the energy barrier for water dissociation. The highly disordered surface and high surface energy of amorphous FeOOH render it highly active. This study presents a viable interface engineering approach for manipulating the reconstruction of the active phase in high-performance perovskite-based electrocatalytic materials.