In-Situ Constructuring of Copper-Doped Bismuth Catalyst for Highly Efficient CO2 Electrolysis to Formate in Ampere-Level

CO₂ electrochemical reduction (CO₂RR) can mitigate environmental issues while providing valuable products, yet challenging in activity, selectivity, and stability. Here, a CuS-Bi₂S₃ heterojunction precursor is reported that can in situ reconstruct to Cu-doped Bismuth (CDB) electrocatalyst during CO₂RR. The CDB exhibits an industrial-compatible current density of −1.1 A cm⁻² and a record-high formate formation rate of 21.0 mmol h⁻¹ cm⁻² at −0.86 V versus the reversible hydrogen electrode toward CO₂RR to formate, dramatically outperforming currently reported catalysts. Importantly, the ultrawide potential region of 1050 mV with high formate Faradaic efficiency of over 90% and superior long-term stability for more than 100 h at −400 mA cm⁻² can also be realized. Experimental and theoretical studies reveal that the remarkable CO₂RR performance of CDB results from the doping effect of Cu which optimizes adsorption of the *OCHO and boosts the structural stability of metallic bismuth catalyst. This study provides valuable inspiration for the design of element-doping electrocatalysts to enhance catalytic activity and durability.     

Tunable and Efficient Tin Modified Nitrogen‐Doped Carbon Nanofibers for Electrochemical Reduction of Aqueous Carbon Dioxide

Efficient and selective earth‐abundant catalysts are highly desirable to drive the electrochemical conversion of CO₂ into value‐added chemicals. In this work, a low‐cost Sn modified N‐doped carbon nanofiber hybrid catalyst is developed for switchable CO₂ electroreduction in aqueous medium via a straightforward electrospinning technique coupled with a pyrolysis process. The electrocatalytic performance can be tuned by the structure of Sn species on the N‐doped carbon nanofibers. Sn nanoparticles drive efficient formate formation with a high current density of 11 mA cm^?2 and a faradaic efficiency of 62% at a moderate overpotential of 690 mV. Atomically dispersed Sn species promote conversion of CO₂ to CO with a high faradaic efficiency of 91% at a low overpotential of 490 mV. The interaction between Sn species and pyridinic‐N may play an important role in tuning the catalytic activity and selectivity of these two materials.     

Electrocatalytic Co-Upcycling of Nitrite and Ethylene Glycol over Cobalt–Copper Oxides

Electrocatalytic nitrite (NO₂⁻) reduction reaction (NO₂⁻RR) for ammonia (NH₃) synthesis is a promising alternative for NO₂⁻ resource utilization. Herein, a dual-site copper-cobalt oxide catalyst is reported for the efficient electrocatalytic reduction of NO₂⁻ to NH₃, exhibiting NH₃ Faradaic efficiency that remained above 95% (0.1 m NaNO₂) over a wide potential window (−0.1 to −0.6 V vs reversible hydrogen electrode, vs RHE). More importantly, the high NH₃ Faradaic efficiency maintains an over 85% (−0.1 to −0.3 V vs RHE) at a low concentration of NaNO₂ (0.01 m ). Theoretical calculations demonstrate that CuO serves the ^*NO₂ to ^*NO and is subsequently converted to NH₃ on Co₃O₄. Coupled anodic ethylene glycol (EG) oxidation reaction endows low cell voltage (ΔU = 480 mV, 10 mA cm⁻²) and energy consumption saving (>23%) in a two-electrode system. This work provides a reference for a co-upcycling electrolyzer for NO₂⁻ and EG.     

Harmonized Physical and Electrochemical Process Design for Densely Dispersed Cu Catalysts on Cu2O Absorbers for Efficient Photoelectrochemical CO2 Reduction Reaction

The photoelectrochemical CO₂ reduction reaction (photo-CO₂RR) is a promising technology to convert CO₂ into high-value-added carbon-based chemicals using a relatively low voltage, which can economically solve the problem of CO₂ emissions. Nevertheless, unlike the conventional electrochemical CO₂RR approach, photo-CO₂RR technology is in its initial development stage. Particularly, when sunlight is applied to photoelectrodes for photo-CO₂RR, severe photocorrosion is unavoidable, resulting in the deterioration of fundamental functions including device long-term stability and conversion performance. This study proposes an innovative two-step catalyst formation strategy to enable the efficient photo-CO₂RR with Cu catalysts prepared using intrinsic photocorrosion of the Cu₂O absorption layer. This approach is based on the harmonized process design of the i) growth of physically generated Cu nanoparticles and ii) construction of improved photoelectrochemical Cu cluster catalysts. The vacuum-evaporated Cu seeds are designed to induce an evenly dispersed electrical path on Cu₂O, and the selectively concentrated electrical field from the Cu seeds provides preferential sites for metallic Cu catalysts in subsequent photoelectrochemical reduction. This harmonized combination process of Cu catalysts on Cu₂O demonstrates a synergistic performance of −1.2 mA cm⁻² at 0 V_RHE with suppression of photocorrosion and produces ≈95% CO product gas (0.4 V_RHE).     

Local Steric Hindrance for CO2 Electroreduction at a Thermodynamic Potential and Wide Working Window

To improve the energy-conversion efficiency and adaptability between a CO₂ electroreduction system and intermittent renewable energy, small onset potentials, and wide working windows are highly important. Here, three indium metal–organic frameworks (In-MOFs) have been projected using different ligands to adjust the local steric hindrance and electronic structure of In nodes, manipulating the whole workflow of CO₂ during electroreduction including local CO₂ transport, adsorption, activation, hydrogenation, and product desorption. Significantly, a CO₂ electroreduction to formate process promoted by 2,5-TDC In-MOF shows an onset potential of −0.1 V versus RHE around the therymodynamic potential, over 90% FE_foramte in a wide current-density window from 0.1 to 0.9 A cm⁻². Driven by solar cells, the system displays a high solar-to-chemical efficiency of 17.39%. In depth mechanism study indicates that the local CO₂ transport and adsorption of all In-MOFs are thermodynamically and kinetically favorable, while the energy barrier of potential-determine step (*HCOOH desorption) is the lowest for 2,5-TDC In-MOF.     

CeNCl-CeO2 Heterojunction-Modified Ni Catalysts for Efficient Electroreduction of CO2 to CO

Renewable-electricity-powered electrochemical CO₂ reduction (CO₂RR) is considered one of the most promising ways to convert exhaust CO₂ into value-added chemicals and fuels. Among various CO₂RR products, CO is of great significance since it can be directly used as feedstock to produce chemical products through the Fischer–Tropsch process. However, the CO₂-to-CO electrocatalytic process is often accompanied by a kinetically competing side reaction: H₂ evolution reaction (HER). Designing electrocatalysts with tunable electronic structures is an attractive strategy to enhance CO selectivity. In this work, a CeNCl-CeO₂ heterojunction-modified Ni catalyst is successfully synthesized with high CO₂RR catalytic performance by the impregnation-calcination method. Benefiting from the strong electron interaction between the CeNCl-CeO₂ heterojunction and Ni nanoparticles (NPs), the catalytic performance is greatly improved. Maximal CO Faradaic efficiency (FE) is up to 90% at −0.8 V (vs RHE), plus good stability close to 12 h. Detailed electrochemical tests and density functional theory (DFT) calculation results reveal that the introduction of the CeNCl-CeO₂ heterojunction tunes the electronic structure of Ni NPs. The positively charged Ni center leads to an enhanced local electronic structure, thus promoting the activation of CO₂ and the adsorption of ^*COOH.     

Fast Charge-Transfer Rates in Li-CO2 Batteries with a Coupled Cation-Electron Transfer Process

Li-CO₂ batteries with a high theoretical energy density (1876 Wh kg⁻¹) have unique benefits for reversible carbon fixation for energy storage systems. However, due to lack of stable and highly active catalysts, the long-term operation of Li-CO₂ batteries is limited to low current densities (mainly <0.2 mA cm⁻²) that are far from practical conditions. In this work, it is discovered that, with an ionic liquid-based electrolyte, highly active and stable transition metal trichalcogenide alloy catalysts of Sb_0.67Bi_1.33X₃ (X = S, Te) enable operation of the Li-CO₂ battery at a very high current rate of 1 mA cm⁻² for up to 220 cycles. It is revealed that: i) the type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, ii) a coupled cation-electron charge transfer process facilitates the carbon dioxide reduction reaction (CO₂RR) occurring during discharge, and iii) the concentration of ionic liquid in the electrolyte controls the number of participating CO₂ molecules in reactions. A combination of these key factors is found to be crucial for a successful operation of the Li-CO₂ chemistry at high current rates. This work introduces a new class of catalysts with potential to fundamentally solve challenges of this type of batteries.     

Room-Temperature Molten Salt-Mediated CsPbI3 Growth for Excellent Photovoltaic Performance

Defects within perovskite have been known to act as the nonradiative recombination centers, negatively impacting the carrier transport, which degrades the photovoltaic performance of perovskite solar cells (PSCs). Therefore, preparing a high-quality perovskite film is of vital significance. To this end, a room-temperature molten salt, dimethylamine formate (DMAFa), is introduced into perovskite precursor solution to regulate the crystallization process of CsPbI₃ films. DMAFa can coordinate with Pb²⁺ as HCOO⁻-Pb²⁺ in the early stages, then HCOO⁻-Pb²⁺ is gradually displaced by I⁻-Pb²⁺ due to its decomposition during the subsequent annealing, thus delaying the crystallization rate, meanwhile, the DMA⁺ can interact with the uncoordinated Pb²⁺ to passivate defects of perovskite films, thereby, forming a high-quality CsPbI₃ film with large grain size and low-defect density. As a result of this strategy, the power conversion efficiency is increased to 20.40%, and the open-circuit voltage is up to 1.21 V. These findings indicate that the introduction of DMAFa offers a fundamental way to achieve high-performance CsPbI₃ PSCs.     

Classification and enzyme kinetics of formate dehydrogenases for biomanufacturing via CO2 utilization

The reversible interconversion of formate (HCOO^?) and carbon dioxide (CO₂) is catalyzed by formate dehydrogenase (FDH, EC 1.17.1.9). This enzyme can be used as a first step in the utilization of CO₂ as carbon substrate for production of high-in-demand chemicals. However, comparison and categorization of the very diverse group of FDH enzymes has received only limited attention. With specific emphasis on FDH catalyzed CO₂ reduction to HCOO^?, we present a novel classification scheme for FDHs based on protein sequence alignment and gene organization analysis. We show that prokaryotic FDHs can be neatly divided into six meaningful sub-types. These sub-types are discussed in the context of overall structural composition, phylogeny of the gene segment organization, metabolic role, and catalytic properties of the enzymes. Based on the available literature, the influence of electron donor choice on the efficacy of FDH catalyzed CO₂ reduction is quantified and compared. This analysis shows that methyl viologen and hydrogen are several times more potent than NADH as electron donors. Hence, the new FDH classification scheme and the electron donor analysis provide an improved base for developing FDH-facilitated CO₂ reduction as a viable step in the utilization of CO₂ as carbon source for green production of chemicals.     

Edge‐Exposed Molybdenum Disulfide with N‐Doped Carbon Hybridization: A Hierarchical Hollow Electrocatalyst for Carbon Dioxide Reduction

Electrochemical CO₂ reduction (CO₂RR) is a promising technology to produce value‐added fuels and weaken the greenhouse effect. Plenty of efforts are devoted to exploring high‐efficiency electrocatalysts to tackle the issues that show poor intrinsic activity, low selectivity for target products, and short‐lived durability. Herein, density functional theory calculations are firstly utilized to demonstrate guidelines for design principles of electrocatalyst, maximum exposure of catalytic active sites for MoS₂ edges, and electron transfer from N‐doped carbon (NC) to MoS₂ edges. Based on the guidelines, a hierarchical hollow electrocatalyst comprised of edge‐exposed 2H MoS₂ hybridized with NC for CO₂RR is constructed. In situ atomic‐scale observation for catalyst growth is performed by using a specialized Si/SiN_x nanochip at a continuous temperature‐rise period, which reveals the growth mechanism. Abundant exposed edges of MoS₂ provide a large quantity of active centers, which leads to a low onset potential of ≈40 mV and a remarkable CO production rate of 34.31 mA cm^?2 with 92.68% of Faradaic efficiency at an overpotential of 590 mV. The long‐term stability shows negligible degradation for more than 24 h. This work provides fascinating insights into the construction of catalysts for efficient CO₂RR.     

Greenhouse gas fluxes over managed grasslands in Central Europe

Central European grasslands are characterized by a wide range of different management practices in close geographical proximity. Site‐specific management strategies strongly affect the biosphere–atmosphere exchange of the three greenhouse gases (GHG) carbon dioxide (CO₂), nitrous oxide (N₂O), and methane (CH₄). The evaluation of environmental impacts at site level is challenging, because most in situ measurements focus on the quantification of CO₂ exchange, while long‐term N₂O and CH₄ flux measurements at ecosystem scale remain scarce. Here, we synthesized ecosystem CO₂, N₂O, and CH₄ fluxes from 14 managed grassland sites, quantified by eddy covariance or chamber techniques. We found that grasslands were on average a CO₂ sink (−1,783 to −91 g CO₂ m⁻² year⁻¹), but a N₂O source (18–638 g CO₂‐eq. m⁻² year⁻¹), and either a CH₄ sink or source (−9 to 488 g CO₂‐eq. m⁻² year⁻¹). The net GHG balance (NGB) of nine sites where measurements of all three GHGs were available was found between −2,761 and −58 g CO₂‐eq. m⁻² year⁻¹, with N₂O and CH₄ emissions offsetting concurrent CO₂ uptake by on average 21 ± 6% across sites. The only positive NGB was found for one site during a restoration year with ploughing. The predictive power of soil parameters for N₂O and CH₄ fluxes was generally low and varied considerably within years. However, after site‐specific data normalization, we identified environmental conditions that indicated enhanced GHG source/sink activity (“sweet spots”) and gave a good prediction of normalized overall fluxes across sites. The application of animal slurry to grasslands increased N₂O and CH₄ emissions. The N₂O‐N emission factor across sites was 1.8 ± 0.5%, but varied considerably at site level among the years (0.1%–8.6%). Although grassland management led to increased N₂O and CH₄ emissions, the CO₂ sink strength was generally the most dominant component of the annual GHG budget.     

The metabolic cost of bicarbonate use in the submerged plant Elodea nuttallii

The aquatic plant Elodea nuttallii (Planch.) St. John has been shown to express plasticity in the source of inorganic carbon it uses for photosynthesis. An investigation was undertaken to determine what effect the switch from CO₂ to HCO₃⁻ use had on the growth of E. nuttallii. Plants were grown under reduced CO₂ availability that favoured the switch, together with control plants (CO₂ at equilibrium with air) that continued to use CO₂ only. The extent to which both sets of plants could utilise HCO₃⁻ was determined (as the ratio of oxygen evolution at pH 9 and 6.5), and several measures of growth were made. Although reduced CO₂ availability produced an increase in HCO₃⁻ utilisation, no differences were found in the measured growth of the plants. Therefore, it was possible to estimate, from the difference between the estimated rate of photosynthesis of the plants utilising HCO₃⁻ and those using CO₂ only, the approximate cost of constructing, maintaining and running the bicarbonate utilisation mechanism in this species as 69 μmol photons m⁻² s⁻¹. This value can be used to estimate an irradiance of circa 80 μmol m⁻² s⁻¹ below which HCO₃⁻ use would not be expected in this species, an irradiance commonly experienced by submerged macrophytes in the field.     

Continuous 3D Titanium Nitride Nanoshell Structure for Solar‐Driven Unbiased Biocatalytic CO2 Reduction

Z‐scheme‐inspired tandem photoelectrochemical (PEC) cells have received attention as a sustainable platform for solar‐driven CO₂ reduction. Here, continuously 3D‐structured, electrically conductive titanium nitride nanoshells (3D TiN) for biocatalytic CO₂‐to‐formate conversion in a bias‐free tandem PEC system are reported. The 3D TiN exhibits a periodically porous network with high porosity (92.1%) and conductivity (6.72 × 10⁴ S m^?1), which allows for high enzyme loading and direct electron transfer (DET) to the immobilized enzyme. It is found that the W‐containing formate dehydrogenase from Clostridium ljungdahlii (ClFDH) on the 3D TiN nanoshell is electrically activated through DET for CO₂ reduction. At a low overpotential of 40 mV, the 3D TiN‐ClFDH stably converts CO₂ to formate at a rate of 0.34 µmol h^?1 cm^?2 and a faradaic efficiency (FE) of 93.5%. Compared to a flat TiN‐ClFDH, the 3D TiN‐ClFDH shows a 58 times higher formate production rate (1.74 µmol h^?1 cm^?2) at 240 mV of overpotential. Lastly, a bias‐free biocatalytic tandem PEC cell that converted CO₂ to formate at an average rate of 0.78 µmol h^?1 and an FE of 77.3% only using solar energy and water is successfully assembled.     

Uncovering Atomic‐Scale Stability and Reactivity in Engineered Zinc Oxide Electrocatalysts for Controllable Syngas Production

In this study, scalable, flame spray synthesis is utilized to develop defective ZnO nanomaterials for the concurrent generation of H₂ and CO during electrochemical CO₂ reduction reactions (CO₂RR). The designed ZnO achieves an H₂/CO ratio of ≈1 with a large current density (j) of 40 mA cm^?2 during long‐term continuous reaction at a cell voltage of 2.6 V. Through in situ atomic pair distribution function analysis, the remarkable stability of these ZnO structures is explored, addressing the knowledge gap in understanding the dynamics of oxide catalysts during CO₂RR. Through optimization of synthesis conditions, ZnO facets are modulated which are shown to affect reaction selectivity, in agreement with theoretical calculations. These findings and insights on synthetic manipulation of active sites in defective metal‐oxides can be used as guidelines to develop active catalysts for syngas production for renewable power‐to‐X to generate a range of fuels and chemicals.     

Nanoporous Au Thin Films on Si Photoelectrodes for Selective and Efficient Photoelectrochemical CO2 Reduction

An Si photoelectrode with a nanoporous Au thin film for highly selective and efficient photoelectrochemical (PEC) CO₂ reduction reaction (CO₂RR) is presented. The nanoporous Au thin film is formed by electrochemical reduction of an anodized Au thin film. The electrochemical treatments of the Au thin film critically improve CO₂ reduction catalytic activity of Au catalysts and exhibit CO Faradaic efficiency of 96% at 480 mV of overpotential. To apply the electrochemical pretreatment of Au films for PEC CO₂RR, a new Si photoelectrode design with mesh‐type co‐catalysts independently wired at the front and the back of the photoelectrode is demonstrated. Due to the superior CO₂RR activity of the nanoporous Au mesh and high photovoltage from Si, the Si photoelectrode with the nanoporous Au thin film mesh shows conversion of CO₂ to CO with 91% Faradaic efficiency at positive potential than the CO₂/CO equilibrium potential.     

Multi-Shell Copper Catalysts for Selective Electroreduction of CO2 to Multicarbon Chemicals

Electrocatalytic CO₂ reduction (CO₂R) coupled with renewable electricity has been considered as a promising route for the sustainability transition of energy and chemical industries. However, the unsatisfactory yield of desired products, particularly multicarbon (C₂₊) products, has hindered the implementation of this technology. This work describes a strategy to enhance the yield of C₂₊ product formation in CO₂R by utilizing spatial confinement effects. The finite element simulation results suggest that increasing the number of shells in the catalyst wil lead to a high local concentration of *CO and promotes the formation of C₂₊ products. Inspired by this, Cu nanoparticles are synthesized with desired hollow multi-shell structures. The CO₂ reduction results confirm that as the number of shells increase, the hollow multi-shell copper catalysts exhibit improved selectivity toward C₂₊ products. Specifically, the Cu catalyst with 4.4-shell achieved a high selectivity of over 80% toward C₂₊ at a current density of 900 mA cm⁻². Evidence from in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy unveils that the multi-shell Cu catalyst exhibits an enhanced *CO_atop coverage and the stronger interaction with *CO_atop compared to commercial Cu, confirming the simulation results. Overall, the work promises an effective approach for boosting CO₂R selectivity toward value-added chemicals.     

Electrocatalytic Reduction of Gaseous CO2 to CO on Sn/Cu‐Nanofiber‐Based Gas Diffusion Electrodes

Earth‐abundant Sn/Cu catalysts are highly selective for the electrocatalytic reduction of CO₂ to CO in aqueous electrolytes. However, CO₂ mass transport limitations, resulting from the low solubility of CO₂ in water, so far limit the CO partial current density for Sn/Cu catalysts to about 10 mA cm^?2. Here, a freestanding gas diffusion electrode design based on Sn‐decorated Cu‐coated electrospun polyvinylidene fluoride nanofibers is demonstrated. The use of gaseous CO₂ as a feedstock alleviates mass transport limitations, resulting in high CO partial current densities above 100 mA cm^?2, while maintaining high CO faradaic efficiencies above 80%. These results represent an important step toward an economically viable pathway to CO₂ reduction.     

Light‐Driven Highly Selective Conversion of CO2 to Formate by Electrosynthesized Enzyme/Cofactor Thin Film Electrode

The highly selective electrochemical reduction of carbon dioxide (CO₂) is reported to formate (HCOO^‐) at a compactly integrated bioelectrode. The enzymatic biocatalytic cathode is fabricated by single‐step electropolymerization of a multifunctional polydopamine film in which enzyme/cofactor couples are uniquely embedded. Interestingly, this thin biohybrid system of nanoscale thickness assures unprecedentedly prolonged catalytic enzyme stability for about two weeks. Mimicking the natural photosynthesis, combination with the photoanode utilizing the water oxidation, steadily produces formate at a faradaic efficiency of 99.18 ± 6.77% with little degradation at least for 1 d under 1 sun illumination and no external bias.     

Effects of redox potential control on succinic acid production by engineered Escherichia coli under anaerobic conditions

The effects of oxido-reduction potential (ORP) control on succinic acid production have been investigated in Escherichia coli LL016. In LL016, two CO₂ fixation pathways were achieved and NAD⁺ supply was enhanced by co-expression of heterologous pyruvate carboxylase (PYC) and nicotinic acid phosphoribosyltransferase (NAPRTase). During anaerobic fermentation, cell growth and metabolite distribution were changed with redox potential levels in the range of −200 to −400 mV. From the results, the ORP level of −400 mV was preferable, which resulted in the high succinic acid concentration (28.6 g/L) and high succinic acid productivity (0.33 g/L/h). Meanwhile, the yield of succinic acid at the ORP level of −400 mV was 39% higher than that at the ORP level of −200 mV. In addition, a higher NADH/NAD⁺ ratio and increased enzyme activities were also achieved by regulating the culture to a more reductive environment, which further enhanced the succinic acid production.