Activity For CO2 Reduction Research Articles

Constructing functionalized carbon quantum dots on amino-rich graphitic carbon nitride to enhance CO2 photocatalytic reduction: Critical role of functional group modulation

Carbon quantum dots (CQDs) decoration have been widely acknowledged as promising strategy in photocatalysis, yet in-depth understanding of the effect of different functionalized CQDs on CO2 photocatalytic reduction is still lacked. Herein, three kinds of functionalized CQDs, i.e. carboxylic CQDs (CCQDs), amino CQDs (NCQDs) and sulfonated CQDs (SCQDs), were homogeneously anchored on amino-rich g-C3N4 (U1W1-CN) to investigate their CO2 reduction behaviors under simulated solar-light illumination. Structural analysis demonstrated that potential amide covalent bonds formed between U1W1-CN and CCQDs, and noncovalent conjugations might exist between U1W1-CN and SCQDs, while strong electrostatic attraction between U1W1-CN and NCQDs. Performance tests showed CQDs decoration greatly enhanced the CO2 reduction activity, with 7%CCQDs/U1W1-CN exhibiting the optimal CO and CH4 productions of 40.94 μmol g−1 and 2.2 μmol g−1 under 4 h light irradiation, markedly higher than those of 7%SCQDs/U1W1-CN and 7%NCQDs/U1W1-CN. After comprehensive analysis, it was found that CCQDs decoration endowed U1W1-CN with better CO2 adsorption and activation. And due to the potential amide covalent bonds formed between CCQDs and U1W1-CN, 7%CCQDs/U1W1-CN delivered the largest electron density and most abundant COOH– intermediates, contributing much to its superior CO2 reduction activity over 7%NCQDs/U1W1-CN and 7%SCQDs/U1W1-CN. It is expected that the critical role of functional group modulation on CQDs in enhancing CO2 photocatalytic reduction revealed in this work can provide valuable insights into the rational design of more advanced photocatalysts for targeted reactions.

Rigidly Axial O Coordination-Induced Spin Polarization on Single Ni-N4-C Site by MXene Coupling for Boosting Electrochemical CO2 Reduction to CO.

Regulating the spin states in transition-metal (TM)-based single-atom catalysts (SACs), such as the TM-Nx-C configurations, is crucial for improving the catalytic activity. However, the role of spin in single Ni atoms facilitating the electrochemical CO2 reduction reaction (CO2RR) has been largely overlooked. Using first-principles simulations, we investigated the electrocatalytic performance of Ni-N4-C SACs vertically stacked on the O-terminated MXene nanosheets for the CO2RR. The terminated O atoms on MXene axially interact with the Ni atom due to significant charge transfer between them. Unlike the pure Ni-N4 site, which lacks spin polarization, the newly formed Ni-N4O configuration breaks the spin degeneracy of Ni d orbitals, dramatically lifting the energy level of spin-down d orbitals relative to that of spin-up d orbitals. As a result, the d electrons of Ni in the two spin channels are rearranged, leading to large net spin moments of 1.4 μB. Compared to the Ni-N4 site, the partially filled minority-spin dz2 orbitals of Ni on Ni-N4O weaken the occupied d-π* orbitals between Ni and *COOH, significantly stabilizing the key intermediate. The detailed reaction mechanisms and energetics show that four MXenes, namely, Hf3C2, Zr3C2, Hf2C, and Zr2C, can induce a large spin on the Ni site, thereby improving catalytic activity for CO2 reduction to CO, with a lower onset potential of about -0.75 V vs SHE compared to pure Ni SACs (-1.17 V) according to the potential-constant model with an explicit solvent environment.

Nonmetallic catalysts with high activity and selectivity for the electrocatalytic reduction of CO2 to CO

The escalating reliance on fossil fuels has intensified CO2 emissions, presenting significant environmental challenges. Electrocatalytic CO2 reduction offers a dual solution by converting CO2 into valuable chemicals, but complex mechanisms limit selectivity and efficiency. This study introduces a nitrogen-doped carbon catalyst, JGNC, synthesized via pyrolysis with predominantly pyrrolic N (8.18% N content). The JGNC catalysts achieved a current density of −770 mA·cm−2 at −1.2 V (V as. RHE) and CO selectivity of 96.55% at −1.1 V (V vs. RHE), surpassing most catalysts. In situ characterizations and theoretical analyses reveal that pyrrolic N lowers the energy barrier for CO2 reduction more effectively than pyridinic and graphitic forms, stabilizing the CO intermediate. These results highlight the potential of pyrrolic N in advancing CO2 reduction technologies, offering promising pathways for developing highly active and selective catalysts.

Highthroughput Screening of CuBi Bimetallic Catalyst Array for Electrocatalytic CO2 Reduction Reaction by Scanning Electrochemical Microscope.

The testing and evaluation of catalysts in CO2 electroreduction is a very tedious process. To study the catalytic system of CO2 reduction more quickly and efficiently, it is necessary to establish a method that can detect multiple catalysts at the same time. Herein, a series of CuBi bimetallic catalysts have been successfully prepared on a single glass carbon electrode by a scanning micropieptte contact method. The application of scanning electrochemical microscopy (SECM) enabled the visualization of the CO2 reduction activity in diverse catalyst micro-points. The SECM imaging with Substrate generation/tip collection (SG/TC) mode was conducted on CuBi bimetallic micro-points, revealing that HER reaction emerged as the prevailing reaction when a low overpotential was employed. While the applied potential was lower than -1.5 V vs. Ag/AgCl, the reduction of CO2 to formic acid became dominant. Increasing the bismuth proportion in the bimetallic catalyst can inhibit the hydrogen evolution reaction at low potential and enhances the selectivity of the CO product at high cathode overpotential. This research offers a novel approach to examining arrays of catalysts for CO2 reduction.

The Positional Effect of an Immobilized Re Tricarbonyl Catalyst for CO2 Reduction.

The storage of renewable energy through the conversion of CO2 to CO provides a viable solution for the intermittent nature of these energy sources. The immobilization of rhenium(I) tricarbonyl molecular complexes is presented through the reductive coupling of bis(diazonium) aryl substituents. The heterogenized complex was characterized through ultra-visible, attenuated total reflectance, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy to probe the electronic structure of the immobilized complex. In addition, studies of cyclic voltammetry, controlled potential electrolysis, and electrochemical impedance spectroscopy were conducted to examine the CO2 reduction activity. The structure and CO2 reduction performance were compared with a previously reported immobilized rhenium(I) tricarbonyl molecular complex to probe the effect of varying the tethering of the aryl substituent from the 5,5'-position to the 4,4'-position of the 2,2'-bipyridine backbone. The immobilized complex on carbon cloth at the 4,4'-position provided excellent selectivity (FECO > 99%) and maximum TONCO and TOFCO values of 3359 and 0.9 s-1, respectively, without the addition of a Bro̷nsted acid source. A nonaqueous flow cell demonstrated the stability of this complex during a 5 h electrolysis. Tethering at the 4,4'-position, compared to the 5,5'-position, yielded lower overall activity for CO2 reduction and was attributed to the difference in growth morphology and formation of aggregations, due to Re-Re dimer formation and π-π stacking interactions within the metallopolymer matrix. For carbon cloth substrates, an optimized catalyst loading was determined to be 44.6 ± 11 nmol/cm2.

Electronic interaction and band alignment between Cu sub-nanometric clusters and ZnIn2S4 nanosheets towards selective photoreduction of CO2 to CO

Engineering the electronic properties of heterogeneous photocatalysts with charge transfer regulated is an effective strategy to boost their CO2 reduction activity. Here, we drew inspiration from the strong metal-support interaction effect, and fabricated ZnIn2S4 supported-Cu sub-nanometric clusters photocatalyst. Within this catalyst, the formed CuS bond would redistribute interfacial charge, resulting in diverse chemical states of Cu atoms and the establishment of Ohmic contact between ZIS and Cu. The built-in electric field of such Ohmic contact benefited the migration of photoexcited electrons from ZIS to Cu. Further mechanistic studies unveiled the crucial role of positively charged Cu atom near the interface in facilitating H2O dissociation, and its adjacent Cu atom at the top-surface adopting a distinct chemical state could activate linear CO2 molecule into a bent configuration. These features substantially lowered energy barriers for CO2 adsorption and subsequent *COOH formation, and Cu-ZIS, accordingly, exhibited a remarkable CO production rate of 60.2 μmol g-1h−1, approximately 20.8-fold enhancement compared to ZIS counterpart.

Synergistic effect between sulfur vacancies and S-scheme heterojunctions in WO3/VS-Zn3In2S6 for enhanced photocatalytic CO2 reduction in H2O vapor

Converting CO2 into CO, CH4, and other hydrocarbons using solar energy presents a viable approach for addressing energy shortages. In this study, photocatalysts with S-deficient WO3/Zn3In2S6 (WO3/VS-ZIS) S-scheme heterojunctions have been successfully synthesized. Under UV–vis light irradiation, 20 %WO3/VS-ZIS demonstrated significantly improved CO2 reduction activity and CH4 selectivity. Detailed characterization and density functional theory (DFT) calculations reveal that the enhanced performance is due to the synergistic optimization of the S-scheme heterojunction and sulfur vacancies (VS) for CO2 reduction. The presence of VS aids in the adsorption and activation of CO2 and enhances the separation of charge carriers. The 2D/2D S-scheme heterostructure assembled with WO3 nanosheets not only accelerates the migration and separation of photoexcited charge carriers but also improves the adsorption of H2O and the formation of VS, thereby increasing the adsorption and activation of CO2 and facilitating the protonation of CO* to produce CH4. This study clarifies the synergistic effect of VS and S-scheme heterostructures in improving photocatalytic performance, offering valuable insights into the photoactivation process of CO2 at VS in S-scheme heterojunctions.

Revealing Real Active Sites in Intricate Grain Boundaries Assemblies on Electroreduction of CO2 to C2+ Products

AbstractAlthough intricate structural assemblies contribute to enhancing the activity of electrocatalytic CO2 reduction (ECR) to C2+ products, blindly coupling multiple design strategies may not yield the expected results, and even inhibit the activity of intrinsic catalytic sites. Therefore, elucidating the promoting or inhibitory effects of each design strategy on the CO2‐to‐C2+ conversion to clarify the real active sites and dynamic oxidation processes is of paramount importance. Here, commonly used grain boundaries (GBs), oxidation states, and alloying strategies are focused on, constructing four different types of catalysts structures: original Cu GBs, oxygen‐enriched grain boundary oxidation (GBO), Ag‐enriched GBO, and Cu/Ag GBs. Multiple operando characterizations reveal that GBs and GBO strengthen the resistance of the oxidative Cu species to the electrochemical reduction. The in situ generated strongly oxidative hydroxyl radicals alter the local reaction environment on the catalyst surface, inducing and stabilizing oxidative Cuδ+ species. Catalytic activity comparisons indicate that the oxidation state of Cu plays a decisive role in the CO2‐to‐C2+ conversion, and the nanoalloy effect tends to favor the CH4 production in intricate GBs assemblies. Theoretical calculations suggest that weak CO adsorption on GBO structures facilitates hydrogenation, promoting C–C coupling toward C2+ products.

M/BiOCl-(M=Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation.

Selective CO2 photoreduction to C2 hydrocarbons is significant but limited by the inadequate adsorption strength of the reaction intermediates and low efficiency of proton transfer. Herein, an ameliorative *CO adsorption and H2O activation strategy is realized via decorating bismuth oxychloride (BiOCl) nanostructures with different metal (Pt, Pd, and Au) species. Experimental and theoretical calculation results reveal that distinct *CO binding energies and *H acquisition abilities of the metal cocatalysts mediate the CO2 reduction activity and hydrocarbon selectivity. The relatively moderate *CO adsorption and *H supply over Pd/BiOCl endows it with the lowest free energy to generate *CHO, leading to its highest activity of hydrocarbon production. Specifically, the Pt cocatalyst can efficiently participate in H2O dissociation to deliver more *H for facilitating the protonation of the *CHO and *CHOH, thereby favoring CH4 production with 76.51% selectivity. A lower *H supply over Pd/BiOCl and Au/BiOCl results in a large energy barrier for *CHO or *CHOH protonation and thus a more thermodynamically favored OC─CHO coupling pathway, which endows them with vastly increased C2 hydrocarbon selectivity of 81.21% and 92.81%, respectively. The understanding of efficient C2 hydrocarbon production in this study sheds light on how materials can be engineered for photocatalytic CO2 reduction.

Zn0.5Cd0.5S/MoTe2 Z-scheme heterojunction with space-separated oxidation-reduction catalytic sites for photocatalytic CO2 reduction

CO2 reduction by photocatalysis into fuel was a promising approach to address environmental and energy-related issues. However, the competition for the oxidation half reaction of H2O greatly limited the decoupling of CO2 reduction reactions. Heterojunction photocatalysts with special spatially separated redox site structures exhibited excellent performance in the photocatalytic production process. This article reports the preparation of chemically bonded Zn0.5Cd0.5S/MoTe2 Z-scheme heterojunction photocatalysts by self-assembly of MoTe2 on the surface of Zn0.5Cd0.5S nanospheres. The results showed that the photocatalytic reduction of CO performance of the optimal Zn0.5Cd0.5S/MoTe2 reached 71.79 μmol⋅g−1, which was 6.9 times that of Zn0.5Cd0.5S. The density functional theory (DFT) calculations and experimental results jointly indicated that the excellent photocatalytic CO2 reduction performance was mainly attributed to the excellent hydrophilicity of the MoTe2 surface, which provided effective water molecule adsorption sites for Zn0.5Cd0.5S/MoTe2. At the same time, it reduced the competition for reduction sites on the surface of Zn0.5Cd0.5S. A strong interface electric field was formed between the Zn0.5Cd0.5S and MoTe2 Z-scheme band interfaces, and the MoS bonds formed between the interfaces serves as an electron transport channel, greatly enhancing photogenerated carriers’ separation and transfer and regulating the kinetics of interface catalytic reactions. The photocatalytic CO2 reduction activity was increased by the heterojunction’s surface and interface working in concert. This work provided insights into designing photocatalyst materials with excellent photocatalytic activity.

Synergistic Effects of the Electric Field Induced by Imidazolium Rotation and Hydrogen Bonding in Electrocatalysis of CO2.

The roles of the ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and water in controlling the mechanism, energetics, and electrocatalytic activity of CO2 reduction to CO on silver in nonaqueous electrolytes were investigated. The first electron transfer occurs to CO2 at reduced overpotentials when it is trapped between the planes of the [EMIM]+ ring and the electrode surface due to cation reorientation as determined from voltammetry, in situ surface-enhanced Raman spectroscopy, and density functional theory calculations. Within this interface, water up to 0.5 M does not induce significant Faradaic activity, opposing the notion of it being a free proton source. Instead, water acts as a hydrogen bond donor, and the proton is sourced from [EMIM]+. Furthermore, this study demonstrates that alcohols with varying acidities tune the hydrogen bonding network in the interfacial microenvironment to lower the energetics required for CO2 reduction. The hydrogen bonding suppresses the formation of inactive carboxylate species, thus preserving the catalytic activity of [EMIM]+. The ability to tune the hydrogen bonding network opens new avenues for advancing IL-mediated electrocatalytic reactions in nonaqueous electrolytes.

Hot Electrons Induced by Localized Surface Plasmon Resonance in Ag/g-C3N4 Schottky Junction for Photothermal Catalytic CO2 Reduction.

Converting carbon dioxide (CO2) into high-value-added chemicals using solar energy is a promising approach to reducing carbon dioxide emissions; however, single photocatalysts suffer from quick the recombination of photogenerated electron-hole pairs and poor photoredox ability. Herein, silver (Ag) nanoparticles featuring with localized surface plasmon resonance (LSPR) are combined with g-C3N4 to form a Schottky junction for photothermal catalytic CO2 reduction. The Ag/g-C3N4 exhibits higher photocatalytic CO2 reduction activity under UV-vis light; the CH4 and CO evolution rates are 10.44 and 88.79 µmol·h-1·g-1, respectively. Enhanced photocatalytic CO2 reduction performances are attributed to efficient hot electron transfer in the Ag/g-C3N4 Schottky junction. LSPR-induced hot electrons from Ag nanoparticles improve the local reaction temperature and promote the separation and transfer of photogenerated electron-hole pairs. The charge carrier transfer route was investigated by in situ irradiated X-ray photoelectron spectroscopy (XPS). The three-dimensional finite-difference time-domain (3D-FDTD) method verified the strong electromagnetic field at the interface between Ag and g-C3N4. The photothermal catalytic CO2 reduction pathway of Ag/g-C3N4 was investigated using in situ diffuse reflectance infrared Fourier transform spectra (DRIFTS). This study examines hot electron transfer in the Ag/g-C3N4 Schottky junction and provides a feasible way to design a plasmonic metal/polymer semiconductor Schottky junction for photothermal catalytic CO2 reduction.

PAN-assisted preparation of Bi2MoO6 with enhanced photocatalytic CO2 reduction performance

In this study, to improve photocatalytic CO2 reduction efficiency of Bi2MoO6-based photocatalysts, Bi2MoO6 (BMO) was synthesized via a solvothermal method with the assistance of polyacrylonitrile (PAN). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were utilized to evaluate the microstructures, phases, and elemental compositions of the samples. Additionally, the separation and migration efficiency of photogenerated charge pairs during the photocatalytic process were analyzed in detail using surface photovoltage spectroscopy (SPS), photoluminescence spectrum (PL), transient photocurrent density (TPR), and electrochemical impedance spectroscopy (EIS). In comparison with the reference sample, the specific surface area of 2 % BMO (mass ratios of PAN/Bi(NO3)3·5H2O is 2 %) has been increased to 39.6 m2/g, which increases by 0.9 times compared to the reference sample. The successful introduction of oxygen vacancies (OVs) in Bi2MoO6 was confirmed by low-temperature electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS), and suitable OVs is favorable for separation and migration of the photogenerated carriers. The experimental results indicate that the separation efficiency of photogenerated carriers in the PAN-BMO photocatalyst is significantly boosted in contrast to the reference sample. Furthermore, all photocatalysts exhibit higher photocatalytic CO2 reduction activity than the reference sample. It is noteworthy that the 2 % BMO sample shows the highest photocatalytic CO2 reduction activity, and the average photocatalytic CO2 reduction yield over the 2 % BMO reaches 2.16 μmol g−1 h−1, which is 2.25 times higher than that on the reference sample (0.96 μmol g−1 h−1). In view of the findings, photocatalytic CO2 reduction mechanism for BMO with OVs was rationally proposed.

The cooperative p-n heterojunction and Schottky junction in Au-decorated hierarchical CuS@SnS2 hollow cubes for boosted charge transport and CO2 photoreduction

During the photocatalytic CO2 reduction process, fast charge transport, abundant active sites, and high visible light utilization in photocatalysts are key to achieving excellent CO2 conversion efficiency. In this work, we have designed and prepared hierarchical CuS@SnS2p-n heterostructure hollow cubes for photocatalytic CO2 reduction. First, a monolayer of CuS was in situ generated on the pre-prepared Cu2O cubes to construct core–shell Cu2O@CuS cubes by sulfidation of Cu2O cubes. The following etching process led to the formation of CuS hollow cubes. Finally, the hierarchical CuS@SnS2p-n heterostructure hollow cubes were obtained by growing SnS2 nanosheets on the CuS hollow cubes. The prepared CuS@SnS2p-n heterostructure hollow cubes showed an improved photocatalytic CO2 reduction activity compared with the bare CuS and SnS2 control samples. The p-n heterojunction formed between SnS2 and CuS as well as its hollow structure enhanced the charge carrier separation efficiency and the light absorption capacity of the hybrid catalyst. Furthermore, after the decoration of Au nanoparticles, the formed Schottky junction further discouraged the charge carrier recombination. Thus, the cooperative p-n heterojunction and Schottky junction greatly facilitated photocatalytic CO2 reduction, and exhibiting the maximum CO and CH4 yields of 140.1 and 77.5 μmol g−1 h−1, respectively. This work presents an efficient design of high-performance catalysts for photocatalytic CO2 reduction.

(Invited) Elucidating the Cation Effect in CO2 Electroreduction Using Non-Metal Cations

Electrochemical reduction of CO2 may enable a promising route for the recycling of CO2 and the sustainable production of chemicals and fuels. Due to the complex electrochemical environment, a deeper understanding of the reaction mechanism, particularly the role of cations in the process, is still needed. It was recently demonstrated that metal cations are essential for the CO2 reduction to CO, by stabilizing the CO2 – intermediate via electrostatic interaction. Here we investigate the cation effect in CO2 reduction using non-metal cations, particularly quaternary ammonium cations, whose size and shape symmetry can be tuned. We select CO2 reduction on Bi catalyst that produces both CO and formate, thus to reveal and compare the effect of cations on the two reaction pathways. Interestingly, the Faradaic efficiency for CO production increased apparently for the electrolyte with larger cations, while the formate Faradaic efficiency showed a weak dependence on the cation size, indicating a reaction-pathway-dependent effect of the cations. We further compared cations with different symmetries and observed a more profound effect of substituted ammonium cations on the CO2 reduction activity and selectivity, which was attributed to the charge distribution and weak hydration shells of the cations that help stabilize reaction intermediates. Our work elucidates the critical role of cations in the CO2 electroreduction catalysis and suggests a method to improve the electrocatalysis with optimized electrolytes.

Aggregation of Homogeneous Porphyrin Catalysts in Organic Electrolyte Broadly Inhibits Electrochemical CO2 Reduction Performance

Metalloporphyrins are widely used as homogeneous electrocatalysts for the production of renewable fuels from abundant feedstocks and sustainable energy. The modularity of porphyrin catalysts has led to the establishment of structure‐function correlations that aid in predicting and optimizing catalytic activity. Although metalloporphyrins are widely known to aggregate due to their planar structure that promotes π–π stacking, it is surprising that the influence of metalloporphyrin aggregation on electrocatalytic performance has not been previously investigated. Herein, we will document the relative aggregation and electrocatalytic activity for CO2 reduction to CO with three structurally related iron meso-phenylporphyrins in commonly used N,N-dimethylformamide (DMF) electrolyte. An inverse dependence of kinetics on catalyst concentration is observed for all three porphyrins based on cyclic voltammetry data. Furthermore, this inhibition extends to bulk electrolysis performance, where up to 75% of the catalyst in a 1 mM solution is inactive compared to in a 0.25 mM solution. This talk will additionally discuss how aggregation is influenced by organic additives, axial ligands, redox state, metal identity, and porphyrin substituents. Overall, this work emphasizes that metalloporphyrins can aggregate severely (even in well-solubilizing organic electrolytes) and that aggregation effects must be considered for optimization of performance and for meaningful catalytic activity comparisons.

Atomic Layer Deposition of Cu Catalysts on Gas Diffusion Electrodes for Electrochemical CO2 Reduction

Electrochemical CO2 conversion is gaining attention as an important process for carbon fixation through the use of renewable electricity to address the climate change crisis. Copper is a unique single-element catalyst that can induce C-C coupling reactions to generate high-value-added compounds. The triple phase boundary has been successfully controlled at the catalyst interface using gas diffusion electrodes (GDEs) over the past few years, resulting in high C-C coupling performance. Therefore, methods to engineer the catalyst interface on the 3D structure of GDE are of significant importance. Generally, the catalyst on the GDE is introduced through physical vaper deposition (PVD) using sputtering or E-beam evaporation, or through solution methods such as spray coating and drop-casting of nano-particles. However, the porous and tortuous 3D structure of the GDE often result in limited conformality and difficulty in obtaining a uniform and controlled infiltration of the catalyst into the support structure.In this study, we synthesized Cu catalysts directly onto GDE surfaces using plasma-enhanced atomic layer deposition (PE-ALD), which allowed for precise tuning of the catalyst size and loading at the nanoscale [1]. The synthesized catalysts were confirmed to be polycrystalline Cu nanoparticles using grazing incidence X-ray diffraction. To demonstrate the advantages of the conformal and tunable control of PE-ALD deposition, we deposited the same areal mass loading of Cu catalyst onto the GDE substrates using PVD, and compared the CO2 reduction activity in an H-cell environment. The PE-ALD Cu catalyst showed more than 3 times higher current density than the PVD catalyst at the same electrode potential, a low (~10%) Faradaic efficiency (FE) for the hydrogen evolution reaction (HER), and greater than 75% FE for C-C coupling to form C2+ products including ethylene and ethanol, which is comparable to the highest performances reported to date for metallic Cu catalysts in a H-cell environment. Furthermore, stable operation was observed for a duration of 15 hours, with minimal changes in activity and selectivity. In conclusion, the introduction of catalysts using PE-ALD on GDE electrodes represents a powerful new synthesis method that can increase both C-C coupling performance and selectivity compared to PVD deposition, due to its adjustable Cu nanoparticle size and high conformality. Reference 1) J. D. Lenef, S.Y. Lee, K. M. Fuelling, K. E. Rivera Cruz, A. Prajapati, D. O. D. Cornejo, T. H. Cho, K. Sun, E. Alvarado, T. S. Arthur, C. A. Roberts, C. Hahn, C. C. L. McCrory, N. P. Dasgupta, Nano Lett. 23, 10779-10787 (2023)

Tuning the Inter-Metal Interaction between Ni and Fe Atoms in Dual-Atom Catalysts to Boost CO2 Electroreduction.

Dual-atom catalysts (DACs) are promising for applications in electrochemical CO2 reduction due to the enhanced flexibility of the catalytic sites and the synergistic effect between dual atoms. However, precisely controlling the atomic distance and identifying the dual-atom configuration of DACs to optimize the catalytic performance remains a challenge. Here, the Ni and Fe atomic pairs were constructed on nitrogen-doped carbon support in three different configurations: NiFe-isolate, NiFe-N bridge, and NiFe bonding. It was found that the NiFe-N bridge catalyst with NiN4 and FeN4 sharing two N atoms exhibited superior CO2 reduction activity and promising stability when compared to the NiFe-isolate and NiFe-bonding catalysts. A series of characterizations and density functional theory calculations suggested that the N-bridged NiFe sites with an appropriate distance between Ni and Fe atoms can exert a more pronounced synergy. It not only regulated the suitable adsorption strength for the *COOH intermediate but also promoted the desorption of *CO, thus accelerating the CO2 electroreduction to CO. This work provides an important implication for the enhancement of catalysis by the tailoring of the coordination structure of DACs, with the identification of distance effect between neighboring dual atoms.

Diiron Complexes with Rigid and Conjugated S-to-S Bridges for Electrocatalytic Reduction of CO2.

Electroreduction of CO2 to value-added low-carbon chemicals is a promising way for carbon neutrality and CO2 utilization. It was found that the diiron complex [(μ-bdt)Fe2(CO)6] (bdt = benzene-1,2-dithiolate) has high catalytic activity for electrocatalytic CO2 reduction. To further study the effect of the S-to-S bridge on the catalytic performances of diiron complexes for electrochemical CO2 reduction, four diiron complexes 1-4 with different rigid and conjugated S-to-S bridges were either selected or designed. The electrocatalytic studies showed that under optimal conditions, 2 with a 2,3-naphthalenedithiolato bridge exhibited the lowest catalytic onset potential (Eonset = -1.75 V vs Fc+/0), while 4 with a diphenyl-1,2-vinylidene bridge displayed the highest catalytic activity (TOFmax = 295 s-1), which is 1.5 times that of [(μ-bdt)Fe2(CO)6]. The controlled potential electrolysis experiments of 4 in 0.1 M MeOH/MeCN at -2.35 V vs Fc+/0 gave a total faradaic yield close to 100%, with selectivities of 77%, 9%, and 14% for HCOOH, CO, and H2, respectively. The mechanism for CO2 reduction was studied using density functional theory, IR spectroelectrochemistry, and electrochemical methods. The results indicate that modifying the structure of the S-to-S bridge is an effective strategy to improve the catalytic performance of diiron complexes for electrocatalytic CO2 reduction.

Control interfacial charge transfer behavior by creating surface defects on structure unit of heterojunction to drive carrier separation for enhancing photocatalytic CO2 reduction

Controlling interfacial charge transfer behavior of heterojunction is an arduous issue to efficiently drive separation of photogenerated carriers for improving the photocatalytic activity. Herein, the interface charge transfer behavior is effectively controlled by fabricating an unparalleled VO-NiWO4/PCN heterojunction that is prepared by encapsulating NiWO4 nanoparticles rich in surface oxygen vacancies (VO-NiWO4) in the mesoporous polymeric carbon nitride (PCN) nanosheets. Experimental and theoretical investigations show that, differing with the traditional p-n junction, the direction of built-in electric field between p-type NiWO4 and n-type PCN is reversed interestingly. The strongly codirectional built-in electric field is also produced between the surface defect region and inside of VO-NiWO4 besides in the space charge region, the dual drive effect of which forcefully propels interface charge transfer through triggering Z-Scheme mechanism, thus significantly improving the separation efficiency of photogenerated carriers. Moreover, the unique mesoporous encapsulation structure of VO-NiWO4/PCN heterostructure can not only afford the confinement effect to improve the reaction kinetics and specificity in the CO2 reduction to CO, but also significantly reduce mass transfer resistance of molecular diffusion towards the reaction sites. Therefore, the VO-NiWO4/PCN heterostructure demonstrates the preeminent activity, stability and reusability for photocatalytic CO2 reduction to CO reaction. The average evolution rate of CO over the optimal 10 %-VO-NiWO4/PCN composite reaches around 2.5 and 1.8 times higher than that of individual PCN and VO-NiWO4, respectively. This work contributes a fresh design approach of interface structure in the heterojunction to control charge transfer behaviors and thus improve the photocatalytic performance.