Redistribution Of Electrons Research Articles

Hierarchical multi-interface Co1-xS/Co9S8@C hollow microsphere for enhancing dielectric polarization as an efficient microwave absorber

Recently, close attention has been devoted to exploring highly efficient microwave absorbing materials (MAMs). Owing to their tunable dielectric properties and controllable structure, materials doped with heteroatoms have been regarded as promising absorbers. Herein, the Co@C, CoSe2@C, and hierarchical Co1-xS/Co9S8@C hollow microspheres were prepared using hydrothermal and subsequent carbonization, selenium, and vulcanization processes, respectively. The existence of anionic sites immensely affects the permittivity and conductivity of a composite. As a result, CoSe2@C and Co1-xS/Co9S8@C hollow microspheres showed improved conductivity and dielectric losses. Particularly, due to the multiphase transformation in the vulcanization process, the Co1-xS/Co9S8@C hollow microsphere possessed numerous heterogeneous interfaces and rich lattice defects, which led to local electronic redistribution and reinforced dielectric polarization. It exhibited a minimum reflection loss (RLmin) of −61.0 dB at a thinner thickness of 2.0 mm. This study contributes to the insight into the polarization loss mechanisms of multi-component and heteroatom doping composites and stimulates the design of high-efficiency MAMs.

Unveiling Atomic-Scaled Local Chemical Order of High-Entropy Intermetallic Catalyst for Alkyl-Substitution-Dependent Alkyne Semihydrogenation.

High-entropy intermetallic (HEI) nanocrystals, composed of multiple elements with an ordered structure, are of immense interest in heterogeneous catalysis due to their unique geometric and electronic structures and the cocktail effect. Despite tremendous efforts dedicated to regulating the metal composition and structures with advanced synthetic methodologies to improve the performance, the surface structure, and local chemical order of HEI and their correlation with activity at the atomic level remain obscure yet challenging. Herein, by determining the three-dimensional (3D) atomic structure of quinary PdFeCoNiCu (PdM) HEI using atomic-resolution electron tomography, we reveal that the local chemical order of HEI regulates the surface electronic structures, which further mediates the alkyl-substitution-dependent alkyne semihydrogenation. The 3D structures of HEI PdM nanocrystals feature an ordered (intermetallic) core enclosed by a disordered (solid-solution) shell rather than an ordered surface. The lattice mismatch between the core and shell results in apparent near-surface distortion. The chemical order of the intermetallic core increases with annealing temperature, driving the electron redistribution between Pd and M at the surface, but the surface geometrical (chemically disordered) configurations and compositions are essentially unchanged. We investigate the catalytic performance of HEI PdM with different local chemical orders toward semihydrogenation across a broad range of alkynes, finding that the electron density of surface Pd and the hindrance effect of alkyl substitutions on alkynes are two key factors regulating selective semihydrogenation. We anticipate that these findings on surface atomic structure will clarify the controversy regarding the geometric and/or electronic effects of HEI catalysts and inspire future studies on tuning local chemical order and surface engineering toward enhanced catalysts.

Al-doped oxide-derived copper catalyst with stable Cu+ site for efficient electrocatalytic CO2 reduction to C2H4

Electrocatalytic carbon dioxide reduction reaction (ECO2RR), a pivotal process converting CO2 into high-value products, plays a crucial role in advancing objectives of carbon neutrality. Within various catalysts, copper-based electrocatalysts hold a unique position as they demonstrate a remarkable aptitude for producing high-carbon (C2+) products. Notably, the well-established Cu+ sites exhibit robust C-C coupling capabilities, particularly in the synthesis of C2H4 products. However, the challenge lies in maintaining the stability of oxide-derived copper under the negative potential operating conditions. In light of this, we use the ion exchange principle to make Al partially replace Cu-BDC, and then get a dopant by high temperature calcination to prepare Al-doped CuO catalyst. It has been demonstrated that the introduction of oxyphilic Al atoms could induce the redistribution of electrons in the CuO matrix and stabilize the presence of Cu+ in the ECO2RR process. This configuration significantly enhances the catalytic performance of CuO for electrochemically converting CO2 into C2H4. Specifically, the optimized Al-CuO catalyst exhibits ∼50 % Faradaic Efficiency for C2H4 (FEC2H4) at −1.377 V vs. RHE, doubling the performance compared to pure CuO. The design and implementation of doping engineering presented in this work propel advancements in the field of electrocatalytic CO2 reduction for C2H4 production, offering a crucial avenue for the development of efficient catalysts.

Activation of MOF Catalysts with Low Steric Hindrance via Undercoordination Chemistry for Efficient Polysulfide Conversion in Lithium–Sulfur Battery

AbstractLithium–sulfur (Li–S) batteries promise high theoretical energy density and cost‐effectiveness but grapple with challenges like the polysulfide shuttle effect and sluggish kinetics. Metal–organic framework (MOF) catalysts emerge as a leading solution, despite limited conductivity and high steric hindrance. This study employs undercoordination chemistry to modify Zn–Co bimetallic MOFs (D‐ZIF L), removing organic ligands from active centers. This process mitigates spatial hindrance, thereby promoting comprehensive contact between sulfur species and metal active centers, consequently enhancing the catalytic efficiency of MOFs. Moreover, undercoordination treatment of the metal active centers induces electron redistribution, augmenting electron density at the Fermi level of the metal elements, thereby ameliorating the intrinsic conductivity. Leveraging these advantages, fabricated Li–S batteries employing D‐ZIF L catalysts exhibited markedly mitigated shuttling effects and accelerated sulfur species conversion kinetics. Notably, a substantial reverse areal capacity of 5.0 mAh cm⁻2 is achieved after 100 cycles with an evaluated sulfur loading of 5.5 mg cm⁻2. Furthermore, a practical pouch cell demonstrated an initial capacity of 1.8 Ah at 85.8 mA with stable cycling for 50 cycles. This study underscores the potential of undercoordination chemistry in the development of highly conductive MOF catalysts with minimized steric hindrance, thereby advancing the prospects of Li–S battery technology.

Europium Oxide Evoked Multisite Synergism to Facilitate Water Dissociation for Alkaline Hydrogen Evolution

AbstractExploring an efficient nonnoble metal catalyst for hydrogen evolution reaction (HER) is critical for industrial alkaline water electrolysis. However, it remains a great challenge due to the additional energy required for H─OH bond cleavage and the lack of enough H2O adsorption sites for most catalysts. Herein, the integration of oxophilic Eu2O3 with NiCo alloy with evoked multisite synergism to facilitate water dissociation for alkaline HER is proposed. The optimized Eu2O3‐NiCo exhibits excellent HER activity with a low overpotential of only 60 mV at 10 mA cm−2 and good electrochemical stability, which is superior to that of Eu2O3‐free NiCo and comparable to benchmark Pt/C. The key roles of Eu2O3 on the enhanced HER performance of Eu2O3‐NiCo are identified by in situ Raman spectroscopy and theoretical calculations. It is discovered that the Eu2O3 with strong oxophilicity facilitates the adsorption of H2O and the breakage of H─OH bonding while evoking the electron redistribution at Eu2O3/NiCo interface and accelerating the Volmer step in alkaline HER. Furthermore, the obtained Eu2O3‐NiCo as both anode and cathode displays excellent overall water‐splitting activity and stability in 1.0 M KOH solution. It is believed that this study provides an important inspiration to design high‐performance electrocatalysts toward HER based on rare‐earth materials.

CoFe hydroxide towards CoP2-FeP4 heterojunction for efficient and long-term stable water oxidation

Electrochemical water splitting stands out as a promising avenue for green hydrogen production, yet its efficiency is fundamentally governed by the oxygen evolution reaction (OER). In this work, we investigated the growth mechanism of CoFe hydroxide formed by in situ self-corrosion of iron foam for the first time and the significant influence of dissolved oxygen in the immersion solution on this process. Based on this, the CoP2-FeP4/IF heterostructure catalytic electrode demonstrates exceptional OER activity in a 1 M KOH electrolyte, with an overpotential of only 253 ± 4 mV (@10 mA cm−2), along with durability exceeding 1000 h. Density functional theory calculations indicate that constructing heterojunction interfaces promotes the redistribution of interface electrons, optimizing the free energy of adsorbed intermediate during the water oxidation process. This research highlights the importance of integrating self-corroding in-situ growth with interface engineering techniques to develop efficient water splitting materials.

Augmented Electrochemical Oxygen Evolution by d-p Orbital Electron Coupling.

While high-entropy alloys, high-entropy oxides, and high-entropy hydroxides, are advanced as a novel frontier in electrocatalytic oxygen evolution, their inherent activity deficiency poses a major challenge. To achieve the unlimited goal to tailor the structure-activity relationship in multicomponent systems, entropy-driven composition engineering presents substantial potential, by fabricating high-entropy anion-regulated transition metal compounds as sophisticated oxygen evolution reaction electrocatalysts. Herein, a versatile 2D high-entropy metal phosphorus trisulfide is developed as a promising and adjustable platform. Leveraging the multiple electron couplings and d-p orbital hybridizations induced by the cocktail effect, the exceptional oxygen evolution catalytic activity is disclosed upon van der Waals material (MnFeCoNiZn)PS3, exhibiting an impressively low overpotential of 240mV at a current density of 10mA cm-2, a minimal Tafel slope of 32mV dec-1, and negligible degradation under varying current densities for over 96 h. Density functional theory calculations further offer insights into the correlation between orbital hybridization and catalytic performance within high-entropy systems, underscoring the contribution of active phosphorus centers on the substrate to performance enhancements. Moreover, by achieving electron redistribution to optimize the electron coordination environment, this work presents an effective strategy for advanced catalysts in energy-related applications.

Tailoring the interfacial electron redistribution of ball-in-ball structured CuO-Co3O4 nanocomposites for synergistic enhancement in hydrolytic dehydrogenation of ammonia borane

Construction of high-efficiency and affordable catalysts for hydrogen production from hydrolysis of ammonia borane is highly desirable, but significant challenges still exist. In this study, a series of ball-in-ball hollow structured CuO-Co3O4 nanocomposites with varied Cu/Co molar ratio were constructed via simple solvothermal method combined with a post-calcination. The CuO-Co3O4 composite featuring a Cu/Co molar ratio of 1: 2 displayed the highest catalytic efficiency, achieving a turnover frequency (TOF) value of 25.0 molH2 molcat.−1 min−1 for AB hydrolysis. An evident synergistic enhancement in catalytic activity was confirmed between CuO and Co3O4. Experimental and theoretical researches uncovered that the enhancement of activity is originated from the electron transfer between Cu and Co ingredients, which is beneficial for the adsorption and activation of H2O and ammonia borane. In addition, the DFT calculations results revealed that the actual active sites for AB hydrolysis in CuO-Co3O4 composite catalyst is the Co site. These findings should provide some insightful recommendations for designing robust and cost-effective composite catalysts for the hydrolytic dehydrogenation of ammonia borane.

Interface Engineering Induced N, P-Doped Carbon-Shell-Encapsulated FeP/NiP2/Ni5P4/NiP Nanoparticles for Highly Efficient Hydrogen Evolution Reaction

Modifying the electronic structure of a catalyst through interface engineering is an effective strategy to enhance its activity in the hydrogen evolution reaction (HER). Interface engineering is a viable strategy to enhance the catalytic activity of transition metal phosphides (TMPs) in the HER process. The interface-engineered FeP/NiP2/Ni5P4/NiP multi-metallic phosphide nanoparticles confined in a N, P-doped carbon matrix was developed by a simple one-step low-temperature phosphorization treatment, which only requires 72 and 155 mV to receive the current density of 10 mA/cm2 in acid and alkaline electrolyte, respectively. This enhanced performance can be primarily attributed to the heterointerface of FeP/NiP2/Ni5P4/NiP multi-metallic phosphides, which promotes electron redistribution and optimizes the adsorption/desorption strength of H* on the active sites. Furthermore, the N, P-doped carbon framework that encapsulates the nanoparticles inhibits their aggregation, leading to an increased availability of active sites throughout the reaction. The results of this study open up a straightforward and innovative approach to developing high-performance catalysts for hydrogen production.

Interface Engineering via Ti3C2Tx MXene Enabled Highly Efficient Bifunctional NiCoP Array Catalysts for Alkaline Water Splitting.

Developing a non-noble metal-based bifunctional electrocatalyst with high efficiency and stability for overall water splitting is desirable for renewable energy systems. We developed a novel method to fabricate a heterostructured electrocatalyst, comprising a NiCoP nanoneedle array grown on Ti3C2Tx MXene-coated Ni foam (NCP-MX/NF) using a dip-coating hydrothermal method, followed by phosphorization. Due to the abundance of active sites, enhanced electronic kinetics, and sufficient electrolyte accessibility resulting from the synergistic effects of NCP and MXene, NCP-MX/NF bifunctional alkaline catalysts afford superb electrocatalytic performance, with a low overpotential (72 mV at 10 mA cm-2 for HER and 303 mV at 50 mA cm-2 for OER), a low Tafel slope (49.2 mV dec-1 for HER and 69.5 mV dec-1 for OER), and long-term stability. Moreover, the overall water splitting performance of NCP-MX/NF, which requires potentials as low as 1.54 and 1.76 V at a current density of 10 and 50 mA cm-2, respectively, exceeded the performance of the Pt/C∥IrO2 couple in terms of overall water splitting. Density functional theory (DFT) calculations for the NCP/Ti3C2O2 interface model predicted the catalytic contribution to interfacial formation by analyzing the electronic redistribution at the interface. This contribution was also evaluated by calculating the adsorption energetics of the descriptor molecules (H2O and the H and OER intermediates).

MOFs-derived CoMn-layered double hydroxide array anchored to Ti3C2Tx MXene nanosheets as efficent catalysts for rechargeable lithium-oxygen batteries

Rechargeable lithium-oxygen batteries (LOBs) are acknowledged as potential candidates for advanced energy storage devices as a result of their considerable theoretical energy densities. Nevertheless, they encounter significant challenges throughout discharging and recharging phases, including the difficult decomposition of Li2O2 products, sluggish reaction kinetics, and limited cycle stability. In this study, an efficient catalyst was synthesized by in situ growth of metal–organic frameworks (MOFs)-derived cobalt manganese layered double hydroxide (CoMn-LDH) array on Ti3C2Tx MXene nanosheets (CoMn-LDH@Ti3C2Tx). The LOBs with CoMn-LDH@Ti3C2Tx cathode demonstrated high discharge specific capacity of 27.61 Ah g−1 at 100 mA g−1 and an extended cycle stability of over 224 cycles at 500 mA g−1. Density functional theory (DFT) computations showed that CoMn-LDH@Ti3C2Tx facilitates electron redistribution, optimising the adsorption energy of intermediates, thereby lowering the energy barriers for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). Consequently, this work presents a multi-level nanostructured catalyst preparation strategy derived from MOFs, offering new insights for the fabrication of efficient electrocatalytic materials.

D-band center engineering of single Cu atom and atomic Ni clusters for enhancing electrochemical CO2 reduction to CO

The rational design of catalysts with atomic dispersion and a deep understanding of the catalytic mechanism is crucial for achieving high performance in CO2 reduction reaction (CO2RR). Herein, we present an atomically dispersed electrocatalyst with single Cu atom and atomic Ni clusters supported on N-doped mesoporous hollow carbon sphere (CuSANiAC/NMHCS) for highly efficient CO2RR. CuSANiAC/NMHCS demonstrates a remarkable CO Faradaic efficiency (FECO) exceeding 90% across a potential range of −0.6 to −1.2 V vs. reversible hydrogen electrode (RHE) and achieves its peak FECO of 98% at −0.9 V vs. RHE. Theoretical studies reveal that the electron redistribution and modulated electronic structure—notably the positive shift in d-band center of Ni 3d orbital—resulting from the combination of single Cu atom and atomic Ni clusters markedly enhance the CO2 adsorption, facilitate the formation of *COOH intermediate, and thus promote the CO production activity. This study offers fresh perspectives on fabricating atomically dispersed catalysts with superior CO2RR performance.

Synergistic coupling of defective Ru nanoclusters with oxygen-ligand-steered Ru single-atoms modifying interfacial water structure and key intermediates bonding toward efficient hydrogen energy conversion

Constructing highly efficient ruthenium (Ru)-based electrocatalysts and understanding their reaction mechanisms for hydrogen energy conversion are highly desirable, but extremely challenge. Herein, we integrate the well-dispersed defective Ru nanoclusters and oxygen-coordinated Ru single atoms into one electrocatalyst (RuSA-O4/RuNC) toward alkaline hydrogen oxidation and evolution reactions (HOR/HER). Synergistic catalytic mechanism of dual-sites has been revealed by in situ ATR-SEIRAS characterization, EDTA/SCN– poisoning experiments and DFT calculations. Benefiting from the electronic redistribution between RuSA-O4 and RuNC sites, the single-atom RuSA-O4 species can act as Lewis acid sites that display strong affinity toward interfacial water via an O-down (H2O↓) conformation and subsequently promote water dissociation/formation as well as hydroxide adsorption. Meanwhile, adjacent defective Ru sites have around thermoneutral value of H adsorption free energy. RuNC works with RuSA-O4 species, collaboratively reducing reaction barriers. As expected, the RuSA-O4/RuNC achieves 20.3 times mass activity of commercial Pt/C for alkaline HOR at 10 mV overpotential and excellent alkaline HER activity with a low overpotential of 22 mV to deliver 10 mA cm−2, as well as considerable HER mass activity of 17.0-times compared to commercial Pt/C at 50 mV overpotential. Besides, the synergistic dual-sites strategy can also be extended to prepare efficient PtSA-O4/PtNC and IrSA-O4/IrNC electrocatalysts.

Trifunctional phosphorus-doped cobalt molybdate catalyst in self-driven coupling systems for synchronized sulfur recovery and hydrogen evolution

This study introduces a self-driven system that effectively achieves synchronized sulfur recovery and hydrogen production using a Zn-air battery. The system ingeniously integrates the sulfur oxidation reaction (SOR) and the hydrogen evolution reaction (HER) into a single, efficient process. Central to this system is the trifunctional phosphorus-doped cobalt molybdate catalyst (P-CoMoO4/NF), which exhibits superior performance in both HER (ηj = 100 = 0.13 V) and SOR (ηj = 100 = 0.30 V) with remarkable stability (∼360 h), reaching 0.64 V at 100 mA cm−2 for simultaneous sulfur ion degradation and hydrogen production. Through density functional theory simulations and extensive characterizations, it has been shown that phosphorus doping in the cobalt molybdate catalyst facilitates electron redistribution, enhancing the catalyst's conductivity, generating more oxygen vacancies, and promoting improved mass and electron transfer. This modification also lowers the energy barrier for adsorbing reaction intermediates, thus increasing the hydrogen production rate and sulfur oxide conversion in this self-powered system. In summary, this research marks a substantial advancement in the development of trifunctional catalysts and proposes an eco-friendly, cost-effective strategy for integrated reaction systems, paving the way for sustainable energy solutions.

Enhanced Li-O2 battery performance using NiS/MoS2 heterostructure by building internal electric field to promote the one-electron oxygen reduction/oxidation

Electrocatalysts with appropriate electron coupling toward LiO2 intermediates can exhibit superior oxygen reduction/evolution reaction kinetics in Li-O2 batteries (LOBs). In this work, a charge redistribution strategy has been developed by constructing NiS/MoS2 heterostructure nanosheet self-assembled hollow microspheres with an internal electric field to regulate the interaction with LiO2 and then improve the electrochemical performance of LOBs. Density functional theory calculations and physicochemical characterizations reveal that the difference of work functions between NiS and MoS2 promotes the electron redistribution in heterointerface via built-in electrical field, leading to increased electron density of interfacial Ni atom, thereby enhancing its electron coupling toward LiO2 intermediates and promoting one-electron oxygen reduction/oxidation reaction kinetics. As a result, the NiS/MoS2-based LOBs exhibit evidently higher discharge capacity and much better cycling performance than the batteries using NiS and MoS2. This work provides a reliable charge redistribution strategy induced by build-in electric field to design efficient catalysts for LOBs.

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes.

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. A detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-Namido complexes using a high-spin ground-state analogue as a spectral model for the 5T2 excited state.

Revealing the characteristics of oxygen evolution reaction performance of NiZn ferrites

Magnetic field-assisted method has been proved as an effective method to improve oxygen evolution reaction performance (OER) of water splitting, however, the essential reason for the improvement of OER performance still remains unclear. Herein, Ni1-xZnxFe2O4 ferrites were prepared by the combination of hydrothermal and calcination method, the magnetic properties, oxygen evolution reaction performance and the effect of applied magnetic field on OER performance were studied and discussed according to the magnetic properties and ion site situation. The magnetic field effect depended on the applied magnetic field strength and the magnetic magnetization density of catalysts, it was attributed to changes of electron state and redistribution of ions in the spinel structure. The overpotential decreased by approximately 50 mV and its double layer capacitance increased about 60 % at 125 mT applied magnetic field. The results provided a newness research view for the domain of electrochemistry.

Phosphorous Vacancy and Built-In Electric Field Effect of Co-Doped MoP@MXene Heterostructures to Tune Catalytic Activity for Efficient Overall Water Splitting.

Developing cost-effective, durable bifunctional electrocatalysts is crucial but remains challenging due to slow hydrogen/oxygen evolution reaction (HER/OER) kinetics in water electrolysis. Herein, a combined engineering strategy of phosphorous vacancy (Vp) and spontaneous built-in electric field (BIEF) is proposed to design novel highly-conductive Co-doped MoP@MXene heterostructures with phosphorous vacancy (Vp-Co-MoP@MXene). Wherein, Co doping regulates the surface electronic structure and charge re-distribution of MoP, Vp induces more defects and active sites, while BIEF accelerates the interfacial charge transfer rate between Vp-Co-MoP and MXene. Therefore, the synergistic integration of Vp-Co-MoP/MXene efficiently decreases activation energy and kinetic barrier, thus promoting its intrinsically catalytic activity and structural stability. Consequently, the Vp-Co-MoP@MXene catalyst displays low overpotentials of 102.3/196.5 and 265.0/320.0mV at 10/50mA cm-2 for HER and OER, respectively. Notably, two-electrode electrolyzers with the Vp-Co-MoP@MXene bifunctional catalysts to achieve 10/50mA cm-2, only need low-cell voltages of 1.57/1.64V in alkaline media. Besides, experimental and theoretical results confirm that the hetero-structure effectively reduces hydrogen adsorption free energy and rate-determining-step energy barrier of OER intermediates, thereby greatly boosting its intrinsically catalytic activity. This work verifies an effective strategy to fabricate efficient non-precious bifunctional electro-catalysts for water splitting via combination engineering of phosphorous vacancy, cation doping, and BIEF.

In situ fabrication of atomically adjacent dual-vacancy sites for nearly 100% selective CH4 production

The photocatalytic CO2-to-CH4 conversion involves multiple consecutive proton-electron coupling transfer processes. Achieving high CH4 selectivity with satisfactory conversion efficiency remains challenging since the inefficient proton and electron delivery path results in sluggish proton-electron transfer kinetics. Herein, we propose the fabrication of atomically adjacent anion-cation vacancy as paired redox active sites that could maximally promote the proton- and electron-donating efficiency to simultaneously enhance the oxidation and reduction half-reactions, achieving higher photocatalytic CO2 reduction activity and CH4 selectivity. Taking TiO2 as a photocatalyst prototype, the operando electron paramagnetic resonance spectra, quasi in situ X-ray photoelectron spectroscopy measurements, and high-angle annular dark-field-scanning transmission electron microscopy image analysis prove that the VTi on TiO2 as initial sites can induce electron redistribution and facilitate the escape of the adjacent oxygen atom, thereby triggering the dynamic creation of atomically adjacent dual-vacancy sites during photocatalytic reactions. The dual-vacancy sites not only promote the proton- and electron-donating efficiency for CO2 activation and protonation but also modulate the coordination modes of surface-bound intermediate species, thus converting the endoergic protonation step to an exoergic reaction process and steering the CO2 reduction pathway toward CH4 production. As a result, these in situ created dual active sites enable nearly 100% CH4 selectivity and evolution rate of 19.4 μmol g-1 h-1, about 80 times higher than that of pristine TiO2. Thus, these insights into vacancy dynamics and structure-function relationship are valuable to atomic understanding and catalyst design for achieving highly selective catalysis.

Amino-Induced CO2 Spillover to Boost the Electrochemical Reduction Activity of CdS for CO Production.

A considerable challenge in CO2 reduction reaction (CO2RR) to produce high-value-added chemicals comes from the adsorption and activation of CO2 to form intermediates. Herein, an amino-induced spillover strategy aimed at significantly enhancing the CO2 adsorption and activation capabilities of CdS supported on N-doped mesoporous hollow carbon sphere (NH2-CdS/NMHCS) for highly efficient CO2RR is presented. The prepared NH2-CdS/NMHCS exhibits a high CO Faradaic efficiency (FECO) exceeding 90% from -0.8 to -1.1V versus reversible hydrogen electrode (RHE) with the highest FECO of 95% at -0.9V versus RHE in H cell. Additional experimental and theoretical investigations demonstrate that the alkaline -NH2 group functions as a potent trapping site, effectively adsorbing the acidic CO2, and subsequently triggering CO2 spillover to CdS. The amino modification-induced CO2 spillover, combined with electron redistribution between CdS and NMHCS, not only readily achieves the spontaneous activation of CO2 to *COOH but also greatly reduces the energy required for the conversion of *COOH to *CO intermediate, thus endowing NH2-CdS/NMHCS with significantly improved reaction kinetics and reduced overpotential for CO2-to-CO conversion. It is believed that this research can provide valuable insights into the development of electrocatalysts with superior CO2 adsorption and activation capabilities for CO2RR application.