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In this study, we aimed to understand the potential role of the gut microbiome in the development of Alzheimers disease (AD). We took a multi-faceted approach to investigate this relationship. Urine metabolomics were examined in individuals with AD and controls, revealing decreased formate and fumarate concentrations in AD. Additionally, we utilised whole-genome sequencing (WGS) data obtained from a separate group of individuals with AD and controls. This information allowed us to create and investigate host-microbiome personalised whole-body metabolic models. Notably, AD individuals displayed diminished formate microbial secretion in these models. Additionally, we identified specific reactions responsible for the production of formate in the host, and interestingly, these reactions were linked to genes that have correlations with AD. This study suggests formate as a possible early AD marker and highlights genetic and microbiome contributions to its production. The reduced formate secretion and its genetic associations point to a complex connection between gut microbiota and AD. This holistic understanding might pave the way for novel diagnostic and therapeutic avenues in AD management.

The presence of oxygen vacancies (Vo) in electrocatalysts plays a significant role in improving the selectivity and activity of CO2 reduction reaction (CO2RR). In this study, 1D material with large surface area is utilized to enable uniform Vo formation on the catalyst. 1D structured indium selenoiodide (InSeI) is synthesized and used as an electrocatalyst for the conversion of CO2 to formate. The electrochemical treatment of InSeI leads to the leaching of Se and I from the catalyst surface and the formation of Vo. The resulting Vo promotes the activity of the CO2RR, which increases the local pH of the catalyst surface and chemically maintains the oxidized metal sites on the catalyst. Owing to these characteristics, activated In wire exhibited remarkable CO2RR activity, thereby surpassing 93% FEformate at 500 mA cm−2, with a maximum of 97.3% FEformate at 100 mA cm−2. Moreover, the catalytic activity remained consistent for over 50 h at 100 mA cm−2 (FEformate >88%). Thus, the findings imply that using 1D materials can facilitate the formation of oxygen vacancies on the catalyst surface and improve the selectivity and durability of CO2RR. This indicates the potential for further research on 1D materials as electrocatalysts. [ABSTRACT FROM AUTHOR]

By integrating glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER), it is possible to produce high-value chemicals at the anode while simultaneously achieving energy-efficient hydrogen production. In this study, the Ni 3 S 2 /NiFe LDH-NF bifunctional catalyst is synthesized through a two-step hydrothermal method. The Ni 3 S 2 /NiFe LDH-NF exhibits a more wrinkled and compact nanosheet structure, which is beneficial for exposing active sites. Specifically, the as-prepared Ni 3 S 2 /NiFe LDH-NF electrode shows excellent catalytic activity for GOR (1.37 V vs. RHE @100 mA cm−2) and HER (−247 mV vs. RHE @100 mA cm−2), as well as high yield (90.3%, achieving formate production rate of 1.8 mmol h−1 cm−2) and selectivity (95.1%) for formate production of GOR. Notably, the two-electrode electrolyzer exhibits prominent activity, requiring only a low cell voltage of 1.63 V to achieve 100 mA cm−2. This work provides new insights into the design of advanced electrocatalysts for low-cost and glycerol-assisted hydrogen production. [Display omitted] • A heterojunction Ni 3 S 2 /NiFe LDH-NF is successfully constructed. • The performance of catalyst is optimized by adjusting the content of sulfourea. • The catalyst displays superhydrophilicity and superaerophobicity. • The as-prepared catalyst exhibits excellent performance for GOR and HER. [ABSTRACT FROM AUTHOR]

Electrolyte plays crucial roles in electrochemical CO2 reduction reaction (e‐CO2RR), yet how it affects the e‐CO2RR performance still being unclarified. In this work, it is reported that Sn‐Zn hybrid oxide enables excellent CO2‐to‐HCOO− conversion in KHCO3 with a HCOO− Faraday efficiency ≈89%, a yield rate ≈0.58 mmol cm−2 h−1 and a stability up to ≈60 h at −0.93 V, which are higher than those in NaHCO3 and K2SO4. Systematical characterizations unveil that the surface reconstruction on Sn‐Zn greatly depends on the electrolyte using: the Sn‐SnO2/ZnO, the ZnO encapsulated Sn‐SnO2/ZnO and the Sn‐SnO2/Zn‐ZnO are reconstructed on the surface by KHCO3, NaHCO3 and K2SO4, respectively. The improved CO2‐to‐HCOO− performance in KHCO3 is highly attributed to the reconstructed Sn‐SnO2/ZnO, which can enhance the charge transportation, promote the CO2 adsorption and optimize the adsorption configuration, accumulate the protons by enhancing water adsorption/cleavage and limit the hydrogen evolution. The findings may provide insightful understanding on the relationship between electrolyte and surface reconstruction in e‐CO2RR and guide the design of novel electrocatalyst for effective CO2 reduction. [ABSTRACT FROM AUTHOR]

Pd–induced electron–migration of Co promotes C–C bond cleavage of glucose for selective production of active intermediate and hydrogen transfer, achieving CO 2 reduction efficiency 12.6–fold of the catalyst–free case. [Display omitted] Combining terrestrial biomass as the reductant with submarine-type hydrothermal environments for CO 2 reduction represents a possible approach for novel energy production systems that sustainably circulate carbon. However, increasing the reductive power of biomass is the main limitation of this potential method. Herein, we demonstrate that Co-doped with small amounts of Pd enhances the reduction of CO 2 by selectively producing an active intermediate from carbohydrates. This catalytic reaction utilized glucose as a reductant to achieve high formate production efficiency (458.6 g kg−1) with nearly 100% selectivity with 7.5 wt% Pd 1 Co 20 / γ –Al 2 O 3 at a moderate temperature of 225 °C. The regulation of the electronic structure of the catalytic Co surface by the dopant Pd plays a key role in promoting the C–C bond cleavage of glucose and hydrogen transfer for CO 2 reduction. The findings presented here indicate that biomass can serve as the hydrogen source for CO 2 reduction and provide insight into the potential utilization of CO 2 in sustainable industrial applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • FOx and HRP were co-immobilized in organic–inorganic hybrid nanoflower. • FOx@HRP showed good catalytic activity owing to spatial localization of enzymes. • FOx@HRP could be applied in the sensitive and colorimetric detection of formate. • FOx@HRP possessed ideal stability and reusability in the detection of formate. Formate is an important environmental pollutant, and meanwhile its concentration change is associated with a variety of diseases. Thus, rapid and sensitive detection of formate is critical for the biochemical analysis of complex samples and clinical diagnosis of multiple diseases. Herein, a colorimetric biosensor was constructed based on the cascade catalysis of formate oxidase (FOx) and horseradish peroxidase (HRP). These two enzymes were co-immobilized in Cu 3 (PO 4) 2 -based hybrid nanoflower with spatial localization, in which FOx and HRP were located in the shell and core of nanoflower, respectively (FOx@HRP). In this system, FOx could catalyze the oxidation of formate to generate H 2 O 2 , which was then utilized by HRP to oxidize 2,2′-azino-bis-3-ethylbenzothiazoline-6-sulphonic acid to yield blue product. Ideal linear correlation could be obtained between the absorbance at 420 nm and formate concentration. Meanwhile, FOx@HRP exhibited excellent detection performance with low limit of detection (6 μM), wide linear detection range (10–900 μM), and favorable specificity, stability and reusability. Moreover, it could be applied in the detection of formate in environmental, food and biological samples with high accuracy. Collectively, FOx@HRP provides a useful strategy for the simple and sensitive detection of formate and is potentially to be used in biochemical analysis and clinical diagnosis. [ABSTRACT FROM AUTHOR]

Electrocatalytic carbon dioxide reduction reaction (CO2RR) to formic acid (HCOOH) is attracted for superfluous CO2 removal and HCOOH production under ambient conditions. Indium‐based catalysts has considered as a good candidate material for CO2RR to HCOOH due to their environmentally friendly features. However, the catalytic efficiency is limited by the poor HCOOH Faradaic efficiency (FE) and high reaction overpotential of electrocatalyst, and the activity and stability of indium‐based catalysts are unsatisfactory, especially in industrial current density that is critical for commercialization. Herein, a fiber Bi‐doped In2O3 was synthesized through electrospinning method, and it demonstrate a FEHCOOH of 88.2% at −1.5 V versus RHE (reversible hydrogen electrode) with partial current density of −21.8 mA cm−2 in H type cell. Specially, the Bi‐In electrocatalyst also reach the industrial current density standard, which can work at −400 mA cm−2 current density with FEHCOOH of 92.7% (yield of HCOOH is 6.9 mmol h−1) in home‐made Flow cell. Importantly, Bi‐In shows 24 h long‐term stability test in −300 mA cm−2. The improvement catalytic activity of Bi‐In catalyst is ascribed to the optimized electronic structure of In site, and the reduced work function value of Bi‐In is beneficial for reducing the formation energy of the key *OCHO intermediates. [ABSTRACT FROM AUTHOR]

The development of catalytic metallodrugs is an emerging field that may offer new approaches to cancer chemotherapeutic design. By exploiting the unique properties of transition metal complexes, in‐cell catalysis can be applied to modulate the cellular redox balance as part of a multi‐targeting mechanism of action. We describe the synthesis and characterization of six coordinatively unsaturated iridium(III) diamine catalysts that are stable at physiological pH in aqueous solution. Reduction of the colorimetric substrate 2,6‐dichlorophenolindophenol by transfer hydrogenation under biologically compatible conditions achieved turnover frequencies up to 63 ± 2 h−1 and demonstrated that the source of hydride (sodium formate) is the limiting reagent, despite being in a 1000‐fold excess of the catalyst. The catalyst showed low in vivo acute toxicity in zebrafish embryos and modest in vitro potency towards cancer cells. When administered alone, the catalyst generated oxidative stress in cells (an effect that was conserved in vivo), but co‐treatment with a nontoxic dose of sodium formate negated this effect. Co‐treatment with sodium formate significantly enhanced catalyst potency in cancer cells (A2780 ovarian and MCF7 breast cancer cells) and drug‐resistant cells (A2780cis and MCF7‐TAMR1) but not in non‐tumorigenic cells (MRC5), demonstrating that a redox‐targeting mechanism may generate selectivity for cancer cells. [ABSTRACT FROM AUTHOR]

The microenvironment within solid tumors often becomes acidic due to various factors associated with abnormal metabolism and cellular activities, including increased lactate production as a result of dysregulated tumor glycolysis. Recently, we have identified multiple tumor microenvironment (TME) factors that potentiate regulatory T (T reg) cell function in evading anti-tumor immunosurveillance. Despite the strong correlation between lactate and acidity, the potential roles of acidity in intratumoral T reg cell adaptation and underlying molecular mechanisms have gone largely unstudied. In this study, we demonstrate that acidity significantly enhances immunosuppressive functions of nT reg cells, but not iT reg cells, without altering the expression of either FoxP3 or the cell surface receptors CD25, CTLA4, or GITR in these cells. Surprisingly, the addition of lactate, often considered a major contributor to increased acidity of the TME, completely abolished the acidity-induced enhancement of nT reg suppressive functions. Consistently, metabolic flux analyses showed elevated basal mitochondrial respiratory capacity and ATP-coupled respiration in acidity-treated nT reg cells without altering glycolytic capacity. Genome-wide transcriptome and metabolomics analyses revealed alterations in multiple metabolic pathways, particularly the one-carbon folate metabolism pathway, with reduced SAM, folate, and glutathione, in nT reg cells exposed to low pH conditions. Addition of a one-carbon metabolic contributor, formate, diminished the acidity-induced enhancement in nT reg cell suppressive functions, but neither SAM nor glutathione could reverse the phenotype. Remarkably, in vitro transient treatment of nT reg cells resulted in sustained enhancement of their functions, as evidenced by more vigorous tumor growth observed in mice adoptively receiving acidity-treated nT reg cells. Further analysis of intratumoral infiltrated T cells confirmed a significant reduction in CD8+ T cell frequency and their granzyme B production. In summary, our study elucidates how acidity-mediated metabolic reprogramming leads to sustained Treg-mediated tumor immune evasion. • Acidity enhances T reg cell suppressive functions independent of lactate in vitro and in vivo. • T reg cell oxidative metabolic capacity increases as a result of exposure to acidity. • Treatment with acidity results in T reg cell transcriptional and metabolic changes in one-carbon folate metabolism. • Exposure to acidity ex vivo for 48 hours facilitates increased T reg suppressive functions against T eff cells in the TME and promotes tumor growth in the MC38 colon cancer model. • Treatment of T reg cells with acidity and formate restores suppressive capacity induced by acidity and decreases tumor burden in the MC38 colon cancer model. [ABSTRACT FROM AUTHOR]

Converting CO2 into high‐value chemical fuels through green photoelectrocatalytic reaction path is considered as a potential strategy to solve energy and environmental problems. In this work, BiVO4/ZIF‐8 heterojunctions are prepared by in‐situ synthesis of ZIF‐8 nanocrystals with unique pore structure on the surface of BiVO4. The experimental results show that the silkworm pupa‐like BiVO4 is successfully combined with porous ZIF‐8, and the introduction of ZIF‐8 can provide more sites for CO2 capture. The optimal composite ratio of 4 : 1‐BiVO4/ZIF‐8 exhibits excellent CO2 reduction activity and the lowest electrochemical transport resistance. In the electrocatalytic system, the formate Faraday efficiency of 4 : 1‐BiVO4/ZIF‐8 at −1.0 V vs. RHE is 82.60 %. Furthermore, in the photoelectrocatalytic system, the Faraday efficiency increases to 91.24 % at −0.9 V vs. RHE, which is 10.8 times higher than the pristine BiVO4. The results show that photoelectric synergism can not only reduce energy consumption, but also improve the Faraday efficiency of formate. In addition, the current density did not decrease during 34 h electrolysis, showing long‐term stability. This work highlights the importance of the construction of heterojunction to improve the performance of photoelectrocatalytic CO2 reduction. [ABSTRACT FROM AUTHOR]

Electrocatalytic oxidation of glycerol, an oversupplied byproduct of the biodiesel industry, into high‐valued chemicals is alluring to diminishing current dependence on fossil energy. Formic acid is an important glycerol oxidation product that serves as a high‐energy‐density fuel and crucial precursor for the fine chemical industry while developing an electrocatalyst to efficiently convert glycerol into formic acid remains a challenge. Herein, a Cu‐doped nickel phosphide (CuxNi2–xP) electrocatalyst, achieving formate productivity of ≈11 mol m−2 h−1 at 1.54 V versus RHE over a broad glycerol concentration range (10–100 mm) is reported, which is greater than threefolds than that of Ni2P. Furthermore, CuxNi2–xP can enhance the cleavage of C─C bond in glycerol, reducing the production of intermediates and thus attaining high selectivity of formate. In situ experiments integrated with density functional theory (DFT) calculation revealed that the doping of Cu can promote the generation of NiIII─OOH species and enrich glycerol substrates in local environments on CuxNi2–xP surface, thus facilitating reaction efficiency. Finally, the study designed a membrane‐free flow electrolyzer for continuous upgrading glycerol to formate, attaining 16.4 mmol of formate coupled with 0.68 L of H2 at 1.75 V in 8 h. [ABSTRACT FROM AUTHOR]

Bismuth-based electrocatalysts for carbon dioxide (CO2) reduction are notable for their high formate selectivity, scalability, affordability, and low toxicity. Here, we introduced a facile spray pyrolysis method to fabricate catalyst-coated gas diffusion electrodes (GDE) in one step. Our study revealed that deposition temperatures significantly affected the morphology, crystal orientation, and impurity of bismuth oxyiodide (BiOI) nanoplates. Specifically, BiOI prepared at 250 °C (BiOI-250) exhibited exceptional Faradaic efficiency (>90%) for formate production at a high current range (100–300 mA cm–2) and demonstrated outstanding stability (>30 h). In situ Raman spectroscopy indicated that BiOI-250's superior performance stemmed from its resilience to microscopic flooding, a failure mechanism observed in low-temperature BiOI. X-ray absorption spectroscopy (XAS) showed that BiOI-250 predominantly consisted of the active Bi2O2CO3 phase, while low-temperature BiOI contained a mixture of Bi2O2CO3 and the less active Bi metal, formed via the reduction of the Bi2O3 impurity. This impurity led to increased catalyst resistivity, uneven potential distribution, and restructuring, contributing to flooding. Our study underscores the crucial role of catalyst structures in determining electrode performance and flooding propensity, offering key insights for optimizing bismuth-based electrocatalysts for CO2 reduction. [ABSTRACT FROM AUTHOR]

The electrochemical CO2 reduction reaction (ECR) is a promising pathway to producing valuable chemicals and fuels. Despite extensive studies reported, improving CO2 adsorption for local CO2 enrichment or water dissociation to generate sufficient H* is still not enough to achieve industrial‐relevant current densities. Herein, we report a “two‐in‐one” catalyst, defective Bi nanosheets modified by CrOx (Bi−CrOx), to simultaneously promote CO2 adsorption and water dissociation, thereby enhancing the activity and selectivity of ECR to formate. The Bi−CrOx exhibits an excellent Faradaic efficiency (≈100 %) in a wide potential range from −0.4 to −0.9 V. In addition, it achieves a remarkable formate partial current density of 687 mA cm−2 at a moderate potential of −0.9 V without iR compensation, the highest value at −0.9 V reported so far. Control experiments and theoretical simulations revealed that the defective Bi facilitates CO2 adsorption/activation while the CrOx accounts for enhancing the protonation process via accelerating H2O dissociation. This work presents a pathway to boosting formate production through tuning CO2 and H2O species at the same time. [ABSTRACT FROM AUTHOR]

A simple and effective synthetic method for (–)-nopinone via oxidation of (+)-myrtenal by oxone in DMF to form 6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl formate was proposed. Subsequent hydrolysis of the formate under basic conditions formed nopinone in preparative yields of 61–67%. [ABSTRACT FROM AUTHOR]

Heated tobacco products (HTPs) are newly developed nicotine delivery systems via the inhalation of mainstream aerosols generated during the heating of tobacco leaf materials. Previous studies have shown that the amount of chemicals generated is much lower than that generated by conventional combustible cigarettes. However, little attention has been paid to formate, a conjugated base of formic acid with potentially toxic effects on human health. This study aims to understand the actual emission levels and behaviour of formate in mainstream aerosols produced by commercially available HTP devices in Japan. Aerosols were generated from four types of devices with regular and menthol-type flavours using a vaping machine following the CRM 81 puffing protocol. Formate was tapped in 5 mM sodium carbonate solution and subsequently analysed using ion chromatography. The results showed that the total emission amount of formate ranged from 0.0027 ± 0.0031 to 0.27 ± 0.055 mg L−1, varying with heating temperature and flavour type. Moreover, the majority of formate existed in a particulate form due to the weak-basic property of the aerosol, and the formate emission level was much greater than the workplace exposure limit for the direct inhalation of mainstream aerosols. The formate in the mainstream aerosol can be considered a health concern, when using "high-temperature type" HTPs over a long period. [ABSTRACT FROM AUTHOR]

The addition of traditional carbon sources (e.g., acetate) could favor heterotrophic overgrowth in partial denitrification coupled with anammox (PD–A) systems, thus hindering the performance and stability of this novel wastewater nitrogen removal technology. Therefore, it is necessary to develop an effective, environmentally friendly, and inexpensive alternative. This study demonstrated the potential of formate to enhance the performance and community stability of PD–A under mainstream conditions. In a laboratory-scale biofilm reactor, formate addition (COD/NO3−–N = 1.75) improved nitrogen removal efficiency (from 72.1 ± 3.5% to 81.7 ± 2.7%), EPS content (from 106.3 ± 8.1 to 163.0 ± 15.5 mg/gVSS) and increased anammox bacteria growth (predominantly Candidatus Brocadia, from 29.5 ± 0.7% to 34.5 ± 5.4%) while maintaining stable heterotrophs dominated by methylotrophic Desulfobacillus. FISH-NanoSIMS revealed a formate uptake using Ca. Brocadia and Desulfobacillus, with Ca. Brocadia being the major contributor to partial nitrate reduction to nitrite. Desulfobacillus can synthesize diverse hydrophobic amino acids and provide key nutrients for Ca. Brocadia. To achieve comparable nitrogen removal, the cost of the formate-driven PD–A process should be 11.2% lower than that of acetate. These results greatly enrich our understanding of C1 metabolism represented by formate in anammox communities and its application in the context of coupling partial denitrification-anammox toward enhanced nitrogen removal in global wastewater treatment systems. [ABSTRACT FROM AUTHOR]

The present work exhibits an efficient strategy to adjust the electron structure of Bi/Bi 2 O 3 -In 2 O 3 @C by the synergistic effects of Bi-In hetero-diatoms and nanoheterostructure. Also, the formed hetero-bridging absorption of *OCHO and d-d orbital coupling effect could regulate the d-band center and improve the DOS around E f , moderating the free energy of intermediates. Thus, the enhance ECO 2 RR performance can be observed. [Display omitted] Electrocatalytic CO 2 reduction reaction (ECO 2 RR) to value-added chemicals is of significant importance to control CO 2 emission and reach carbon neutrality. Herein, Bi/Bi 2 O 3 -In 2 O 3 @C electrocatalyst with nanosheet arrays is successfully fabricated by a facile solvothermal with subsequent calcination process. It is found that the electron structure of Bi/Bi 2 O 3 -In 2 O 3 @C can be adjusted by the synergistic effects of Bi-In hetero-diatoms, which can significantly enhance its inherent catalytic activity. As expected, it requires a maximum HCOOH faradaic efficiency (FE HCOOH) of 97.6 % at −1.1 V vs. Reversible Hydrogen Electrode (RHE), which further delivers over 90 % at a wide potential range of −0.8 to −1.4 V vs. RHE, and exhibits high stability of 90.1 % over 60-h long-term test. In-situ Raman analysis is performed to explore the mechanism of its excellent stability. Meanwhile, in-situ attenuated total reflection-Fourier-transform infrared (ATR-FTIR) analysis combined with theoretical calculations reveal that the hetero-bridging absorption of *OCHO and d-d orbital coupling effect can regulate d-band center of Bi/Bi 2 O 3 -In 2 O 3 @C and improve its density of states around E f , moderating free energy of intermediates, thereby the improved formate production performance can be seen. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cu clusters with the diameter of ∼1.0 nm was fabricated and coordinated with B, N atoms in porous carbon matrix. • The catalyst showed stable 70 % FE under 20.8 mA cm−2 during 12 h testing in CO 2 RR to formate. • The overall catalytic performance of Cu/BN-C was superior to other Cu-based catalysts. • DFT revealed the synergy between Cu clusters and B, N by enhancing the charge density of Cu. • This research highlighted the importance of synergistic effects of Cu size effect and heteroatoms coordination. Electrochemical CO 2 conversion into formate by intermittent renewable electricity, presents a captivating prospect for both the storage of renewable electrical energy and the utilization of emitted CO 2. Typically, Cu-based catalysts in CO 2 reduction reactions favor the production of CO and other by-products. However, we have shifted this selectivity by incorporating B, N co-doped carbon (BNC) in the fabrication of Cu clusters. These Cu clusters are regulated with B, N atoms in a porous carbon matrix (Cu/BN-C), and Zn2+ ions were added to achieve Cu clusters with the diameter size of ∼1.0 nm. The obtained Cu/BN-C possesses a significantly improved catalytic performance in CO 2 reduction to formate with a Faradaic efficiency (FE) of up to 70 % and partial current density (j formate) surpassing 20.8 mA cm−2 at −1.0 V vs RHE. The high FE and j formate are maintained over a 12-hour. The overall catalytic performance of Cu/BN-C outperforms those of the other investigated catalysts. Based on the density functional theory (DFT) calculation, the exceptional catalytic behavior is attributed to the synergistic effect between Cu clusters and N, B atoms by modulating the electronic structure and enhancing the charge transfer properties, which promoted a preferential adsorption of HCOO* over COOH*, favoring formate formation. [ABSTRACT FROM AUTHOR]

InBiO 6 catalyst is employed for the electroreduction of CO 2. In 2 O 3 /Bi 2 O 3 interface effects exhibit low negative potential and high formate Faradaic efficiency. The study described presents an effective approach for developing high-performance CO 2 reduction electrocatalysts derived from metal-organic frameworks. [Display omitted] • InBiO 6 two-phase co-existing composites was designed for CO 2 electroreduction. • High FE formate (>80 %) in a wide potential window (−0.76 ∼ −1.26 V vs. RHE). • Long-term stability of 317h in H-type cell. • The introduction of Bi changes the electronic environment around In and activates the In sites. • DFT calculations reveal that the heterostructure benefit formate production. The electrochemical reduction of CO 2 (ERCO 2) has emerged as one of the most promising methods for achieving both renewable energy storage and CO 2 recovery. However, achieving both high selectivity and stability of catalysts remains a significant challenge. To address this challenge, this study investigated the selective synthesis of formate via ERCO 2 at the interface of In 2 O 3 and Bi 2 O 3 in the InBiO 6 composite material. Moreover, InBiO 6 was synthesized using indium-based metal–organic frameworks as precursor, which underwent continuous processing through ion exchange and thermal reduction. The results revealed that the formate Faradaic efficiency (FE formate) of InBiO 6 reached nearly 100 % at −0.86 V vs. reversible hydrogen electrode (RHE) and remained above 90 % after continuous 317-h electrolysis, which exceeded those of previously reported indium-based catalysts. Additionally, the InBiO 6 composite material exhibited an FE formate exceeding 80 % across a wide potential range of 500 mV from −0.76 to −1.26 V vs. RHE. Density-functional theory analysis confirmed that the heterogeneous interface of InBiO 6 played a role in achieving optimal free energies for *OCHO on its surface. Furthermore, the addition of Bi to the InBiO 6 matrix facilitated electron transfer and altered the electronic structure of In 2 O 3 , thereby enhancing the adsorption, decomposition, and formate production of *OCHO. [ABSTRACT FROM AUTHOR]

[Display omitted] Electrochemical CO 2 reduction (ECO 2 R) to value-added chemicals offers a promising approach to both mitigate CO 2 emission and facilitate renewable energy conversion. We demonstrate a solar energy powered ECO 2 R system operating at a relatively large current density (57 mA cm−2) using In 2 O 3 nanosheets (NSs) as the cathode and a commercial perovskite solar cell as the electricity generator, which achieves the high solar to formate energy conversion efficiency of 6.6 %. The significantly enhanced operative current density with a fair solar energy conversion efficiency on In 2 O 3 NSs can be ascribed to their high activity and selectivity for formate production, as well as the fast kinetics for ECO 2 R. The Faradic efficiencies (FEs) of formate In 2 O 3 NSs are all above 93 %, with the partial current density of formate ranging from 2.3 to 342 mA cm−2 in a gas diffusion flow cell, which is among the widest for formate production on In-based catalysts. In-situ Raman spectroscopy and density functional theory simulations reveal that the exceptional performances of formate production on In 2 O 3 NSs originates from the presence of abundant low coordinated edge sites, which effectively promote the selective adsorption of *OCHO while inhibiting *H adsorption. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A visible‐light‐induced and efficient one‐pot synthesis of β‐hydroxysulfides from olefins, thiosulfonates and HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed. A plausible radical involved mechanism is proposed. During the reaction process, formates play a crucial role: first, as donors in the EDA complex; second, as providers of the hydrogen source; and third, by generating CO2•– to reduce peroxide intermediates, leading to the formation of β‐hydroxysulfides. In contrast to the previously reported thiol‐oxygen co‐oxidation reactions, this simple and sustainable approach features mild reaction conditions, operational simplicity, odorless and excellent functional group tolerance. [ABSTRACT FROM AUTHOR]

Increasing atmospheric carbon dioxide levels, a reduction of arable land area and the dependence of first and second generation biotechnology feedstocks on agricultural products, call for alternative, sustainable feedstock sources for industrial applications. The direct use of CO2 or conversion of CO2 into other single carbon (C1) sources have great potential as they might help to reduce carbon emissions and do not compete with agricultural land use. Here we discuss the microbial use of C1 carbon sources, their potential applications in biotechnology, and challenges towards sustainable C1-based industrial biotechnology processes. We focus on methanol, formic acid, methane, syngas, and CO2 as feedstocks for bioprocesses, their assimilation pathways, current and emerging applications, and limitations of their application. This mini-review is intended as a first introduction for researchers who are new to the field of C1 biotechnology.

Renewable electricity shows immense potential as a driving force for the carbon dioxide reduction reaction (CO2RR) in production of formate (HCOO−) at industrial current density, providing a promising path for value‐added chemicals and chemical manufacturing. However, achieving high selectivity and stable production of HCOO− at industrial current density remains a challenge. Here, we present a robust Bi0.6Cu0.4 NSs catalyst capable of regenerating necessary catalytic core (Bi−O) through cyclic voltammetry (CV) treatment. Notably, at 260 mA cm−2, faradaic efficiency of HCOO− reaches an exceptional selectivity to 99.23 %, maintaining above 90 % even after 400 h, which is longest reaction time reported at the industrial current density. Furthermore, in stability test, the catalyst was constructed by CV reconstruction to achieve stable and efficient production of HCOO−. In 20 h reaction test, the catalyst has a rate of HCOO− production of 13.24 mmol m−2 s−1, a HCOO− concentration of 1.91 mol L−1, and an energy consumption of 129.80 kWh kmol−1. In situ Raman spectroscopy reveals the formation of Bi−O structure during the gradual transformation of catalyst from Bi0.6Cu0.4 NBs to Bi0.6Cu0.4 NSs. Theoretical studies highlight the pivotal role of Bi−O structure in modifying the adsorption behavior of reaction intermediates, which further reduces energy barrier for *OCHO conversion in CO2RR. [ABSTRACT FROM AUTHOR]

Bi‐based electrocatalysts have attracted high attention due to their high selectivity for formate, low cost, and high biocompatibility. Surface modification with halides can adjust the surface charge distribution of metal catalysts, thereby regulating the binding force of the intermediate. Organic‐inorganic hybrid bismuth halides provide an alternative, especially low dimensional structures. Herein, zero‐dimensional hybrid bismuth halides containing Bi4I16 units (denoted as Bi4I16) was recommended as pre‐catalyst due to the Bi ⋅ ⋅ ⋅ Bi spacing in Bi4I16 is 4.760 Å, nearly equaling to the Bi ⋅ ⋅ ⋅ Bi spacing in rhombohedral Bi (4.750 Å). The equal spacing may be more beneficial for the electricity‐driven in situ conversion and rearrangement of Bi atoms in the catalytic process. As a contrast, zero‐dimensional bismuth halide containing Bi2I9 units (denoted as Bi2I9) with shorter Bi ⋅ ⋅ ⋅ Bi spacing (4.2415 Å) was prepared. The working electrode prepared by Bi4I16 ink was measured for CO2RR, and the partial formate current density can reach 8.2 mA cm−2 at −1.1 V vs RHE. The Bi4I16 catalyst delivers a maximum Faradaic Efficiency (FE, ~80 %) for formate at −0.86 V vs RHE and maintain a FE higher than 78.5 % after 16 h. [ABSTRACT FROM AUTHOR]

Tuning the lattice strain of catalysts represents a powerful strategy to alter their electronic structures and ultimately regulate catalytic performance. Electrocatalytic CO2 reduction is a promising avenue to accomplish the carbon‐neutral cycle, however, there still lacks a distinct and systematic understanding of the lattice strain effect in CO2 electrochemical conversion. In this work, the influence of lattice strain on Bi (012) facets to formate production is studied. The pre‐executed density functional theory (DFT) calculations reveal that lattice compression promotes the wrinkling of exposed Bi surface and increases the total density of state (DOS) of active sites at the Fermi level. As the gradual intensification of lattice contraction, the selectivity of CO2 reduction exhibits a volcanic alteration, with an optimal lattice contraction of 3%. Experimentally synthesized Bi2O2CO3/Bi heterogeneous catalyst confirms the effect of lattice compression. When compression reaches −3.04% on Bi (012) facets, the catalyst possesses the highest Faraday efficiency (FE) of 96.17% at −1.2 VRHE and an industrially scalable current density of −600 mA cm−2. Additionally, in seawater‐based electrolysis, the catalyst also exhibits excellent remarkable FE of 95.43% of formate production. [ABSTRACT FROM AUTHOR]

Liquid metal alloys can accumulate specific solute metal atoms on their surface, creating distinct quasi‐ordered atomic layers. Such atomic layers can be tuned by varying the alloy composition to form catalytic interfaces suited for multi‐step reactions. Here, the surface enrichment in gallium‐indium alloys is studied and utilized for carbon dioxide (CO2) electrochemical reduction. The results show that adding a small amount of indium (16.8 at%) to gallium leads to a significant indium enrichment of >83 at% on the topmost layer of the alloy. This enrichment dictates the CO2 conversion pathway, leading to 98% faradaic efficiency toward formate at −1.90 V vs reversible hydrogen electrode (RHE). This study produces unprecedented insights into key interfacial processes and lays the foundation for significant further work within the areas of catalysis and liquid metals. [ABSTRACT FROM AUTHOR]

Carbon dioxide (CO2) adsorption and electron transport play an important role in CO2 reduction reaction (CO2RR). Herein, we have demonstrated a new class of diverse hollow ZnSnOx (ZSO) through the amorphization of hydroxides to enhance CO2 adsorption and accelerate electron transport. The amorphization is occurred by calcination process, as indicated by Fourier transform infrared spectroscopy and Raman spectra. In particular, the ZnSnOx hollow spheres (ZSO HSs) achieve a high Faradaic efficiency (FE) of HCOOH up to 92.7 % at best, outperforming the commercial ZSO (Comm. ZSO, 85.7 %). ZSO HSs also exhibit durable stability with negligible activity decay after 10 h of successive electrolysis. In‐situ attenuated total reflectance infrared absorption spectroscopy further reveals strong adsorption of CO2 and rapid intermediate configuration transformation in amorphous ZSO HSs. This work demonstrates the practical application of ZSO for CO2RR and provides a new insight to create efficient CO2RR electrocatalysts. [ABSTRACT FROM AUTHOR]

Electrocatalytic glycerol oxidation reaction (GOR) stands out as an economical and prospective technology to replace oxygen evolution reaction for co‐producing high‐valued chemicals and hydrogen (H2). Regulating the adsorption of glycerol (GLY) and hydroxyl (OH) species is of great significance for improving the GOR performance. Herein, a hierarchical p–n heterojunction by combining Co‐metal organic framework (MOF) nanosheets with CuO nanorod arrays (CuO@Co‐MOF) is developed to realize the optimization on GOR. Specifically, CuO@Co‐MOF electrode exhibits superior performance with a conversion of 98.4%, formic acid (FA) selectivity of 87.3%, and Faradaic efficiency (FE) of 98.9%. The flow‐cell system with the bifunctional CuO@Co‐MOF electrode for pairing GOR with the hydrogen evolution reaction (HER) reveals better energy conversion efficiency. Experimental results and theoretical calculations unravel the redistributed electric field by introducing Co‐containing species that contribute to the improved performance, which not only enhances the OH adsorption but also modulates the excessive GLY adsorption of CuO, thus reducing reaction energy barriers of FA desorption. Simultaneously, finite element analysis reveals that the novelty hierarchical structure can increase the concentration of OH− and facilitate the mass transfer of OH− in the solution. [ABSTRACT FROM AUTHOR]

Terephthalic acid (TPA) was recovered by alkaline hydrolysis of waste polyethylene terephthalate (PET) bottles. TPA recovered was used to prepare Sn-based catalyst by solvothermal method. For comparison, commercial TPA was also used to prepare Sn-based catalyst. The catalysts were used for the electrochemical reduction of CO2 to formate. Both the catalysts were found to possess nanoflake morphology, and were highly porous in nature with Brunauer–Emmett–Teller (BET) surface area of 211.4 and 239.4 m2/g for commercial and PET derived TPA-based Sn catalysts, respectively. The catalyst made from the waste PET bottles derived TPA was found to be more effective than the one obtained from the commercial TPA. The Faradaic efficiency obtained for the formation of formate was 68.4% at potential − 1.8 V (vs Ag/AgCl) and current density of 13.5 mA/cm2, when catalyst was synthesized using waste PET derived TPA. High activity of the electrocatalysts was attributed to higher capacitance, and lower resistance of the catalysts. [ABSTRACT FROM AUTHOR]

The increasing levels of carbon dioxide (CO2) in the atmosphere, primarily due to the use of fossil fuels, pose a significant threat to the environment and necessitate urgent action to mitigate climate change. Carbon capture and utilization technologies that can convert CO2 into economically valuable compounds have gained attention as potential solutions. Among these technologies, biocatalytic CO2 hydrogenation using bacterial whole cells shows promise for the efficient conversion of CO2 into formate, a valuable chemical compound. Although it was discovered nearly a century ago, comprehensive reviews focusing on the utilization of whole‐cell bacteria as the biocatalyst in this area remain relatively limited. Therefore, this review provides an analysis of the progress, strategies, and key findings in this field. It covers the use of living cells, resting cells, or genetically modified bacteria as biocatalysts to convert CO2 into formate, either naturally or with the integration of electrochemical and protochemical techniques as sources of protons and electrons. By consolidating the current knowledge in this field, this review article aims to serve as a valuable resource for researchers and practitioners interested in understanding the recent progress, challenges, and potential applications of bacterial whole cell catalyzed CO2 hydrogenation into formate. [ABSTRACT FROM AUTHOR]

Light‐driven carboxylation offers a promising approach for synthesizing valuable fine chemicals under mild conditions. Here we disclose a heterogeneous photocatalytic strategy of C(sp2)−H activation of formate for hydrocarboxylation of alkenes over zinc indium sulfide (ZnIn2S4) under visible light. This protocol functions well with a variety of substituted styrenes with good to excellent yields; it also works for unactivated alkenes albeit with lower yields. Mechanistic studies confirm the existence of CO2⋅− as a key intermediate. It was found that C(sp2)−H activation of formate is induced by S⋅ species on the surface of ZnIn2S4 via hydrogen atom transfer (HAT) instead of a photogenerated hole oxidation mechanism. Moreover, both cleavage of the C(sp2)−H of HCOO− and formation of a benzylic anion were found to be involved in the rate‐determining step for the hydrocarboxylation of styrene. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P−O)δ− modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P−O)δ− has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P−O)δ− modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P−O)δ− modified oxide‐derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm−2 and a cathodic potential of −1.2 V vs. RHE in an alkaline electrolyte. [ABSTRACT FROM AUTHOR]

[Display omitted] The potential for directly converting CO 2 to valuable liquid fuels utilizing green and renewable electricity has sparked significant interest in CO 2 electroreduction (CO 2 RR). In recent years, CO 2 conversion to formate/formic acid (HCOO−/HCOOH) has witnessed fast growth due to its economic and technological viability combined with the development of highly selective catalysts and practical electrolyzes. In this review, we summarize and discuss recent advances in HCOOH generation from CO 2 reduction in terms of (1) the rationale behind choosing HCOOH as a CO 2 electroreduction product, (2) mechanistic pathways to form HCOOH, (3) novel electrocatalyst developments for enhanced HCOOH production, and (4) electrolyzer designs that tackle practical challenges in scalability, reaction rate, and product impurities. Finally, a brief outlook on future opportunities in this field is offered to accelerate the industrialization of CO 2 RR to HCOOH. [ABSTRACT FROM AUTHOR]

The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) is extensively regarded as a promising strategy to reach carbon neutralization. Copper sulfide (CuS) has been widely studied for its ability to produce C1 products with high selectivity. However, challenges still remain owing to the poor selectivity of formate. Here, a Bi/CeO2/CuS composite was synthesized using a simple solvothermal method. Bi/CeO2-decorated CuS possessed high formate selectivity, with the Faraday efficiency and current density reaching 88% and 17 mA cm-2, respectively, in an H-cell. The Bi/CeO2/CuS structure significantly reduces the energy barrier formed by OCHO*, resulting in the high activity and selectivity of the CO2 conversion to formate. Ce4+ readily undergoes reduction to Ce3+, allowing the formation of a conductive network of Ce4+/Ce3+. This network facilitates electron transfer, stabilizes the Cu+ species, and enhances the adsorption and activation of CO2. Furthermore, sulfur catalyzes the OCHO* transformation to formate. This work describes a highly efficient catalyst for CO2 to formate, which will aid in catalyst design for CO2RR to target products. [ABSTRACT FROM AUTHOR]

An hydrophobized gas-diffusion electrode with a tin catalyst deposited onto acetylene black A437E is tested with the aim of elucidation of its potential in intensifying the CO2 electroreduction to formate in acidic and alkaline aqueous solutions. Porous electrodes with the fluoroplastic content of 40 wt %, a thickness of 0.5 mm, porosity of 60 vol %, and the tin content ≈0.7 mg/cm2 of the total electrode surface are studied. It is shown that this type of electrodes can be used in electroreduction of CO2 at a current density of up to 900 mA/cm2, a temperature of 25–55°C with the current efficiency from 74 to 96% with respect to formate. The 4 h electrolysis at a current density of 190 mA/cm2 produces a solution with the potassium formate concentration of 1.58 M. This is accompanied by the increase in the capacitance of the electric double layer from 7 to 17 mF/cm2 and the decrease in the current efficiency from 96 to 58%. [ABSTRACT FROM AUTHOR]

The development of synthetic microorganisms that could use one-carbon compounds, such as carbon dioxide, methanol, or formate, has received considerable interest. In this study, we engineered Pichia pastoris and Saccharomyces cerevisiae to both synthetic methylotrophy and formatotrophy, enabling them to co-utilize methanol or formate with CO 2 fixation through a synthetic C1-compound assimilation pathway (MFORG pathway). This pathway consisted of a methanol-formate oxidation module and the reductive glycine pathway. We first assembled the MFORG pathway in P. pastoris using endogenous enzymes, followed by blocking the native methanol assimilation pathway, modularly engineering genes of MFORG pathway, and compartmentalizing the methanol oxidation module. These modifications successfully enabled the methylotrophic yeast P. pastoris to utilize both methanol and formate. We then introduced the MFORG pathway from P. pastoris into the model yeast S. cerevisiae , establishing the synthetic methylotrophy and formatotrophy in this organism. The resulting strain could also successfully utilize both methanol and formate with consumption rates of 20 mg/L/h and 36.5 mg/L/h, respectively. The ability of the engineered P. pastoris and S. cerevisiae to co-assimilate CO 2 with methanol or formate through the MFORG pathway was also confirmed by 13C-tracer analysis. Finally, production of 5-aminolevulinic acid and lactic acid by co-assimilating methanol and CO 2 was demonstrated in the engineered P. pastoris and S. cerevisiae. This work indicates the potential of the MFORG pathway in developing different hosts to use various one-carbon compounds for chemical production. [Display omitted] • A synthetic C1-compound assimilation pathway composed by methanol-formate oxidation module and the rGly pathway. • The MFORG pathway enables P. pastoris and S. cerevisiae to Co-utilize Methanol or formate coupled with CO 2 fixation. • Methanol bioconversion to the high value-added compounds lactic acid and 5-aminolevulinic acid was achieved. [ABSTRACT FROM AUTHOR]

In 2022, Beller and coworkers achieved the reversible hydrogenation of CO2 to formic acid using a Mn(I)–PN5P complex with excellent activity and reusability of the catalyst. To understand the detailed mechanism for the reversible hydrogen release–storage process, especially the effects of the transition metal center in this process, we employed DFT calculations according to which Ru(II) and Fe(II) are considered as two alternatives to the Mn(I) center. Our computational results showed that the production of formic acid from CO2 hydrogenation is not thermodynamically favorable. The reversible hydrogen release–storage process actually occurs between CO2/H2 and formate rather than formic acid. Moreover, Mn(I) might not be a unique active metal for the reversible hydrogenation of CO2 to formate; Ru(II) would be a better option. [ABSTRACT FROM AUTHOR]

Pb SA -Cu/PC with a three-dimensional structure was demonstrated as an efficient CO 2 reduction catalyst to formate. Pb inhibited the formation of COOH*, reduced the energy barrier of rate determining step in the formate formation process, and achieved 97% high formate selectivity. [Display omitted] • Pb SA100 -Cu/CP catalyst is developed by an economical and low-energy method. • The FE formate is 97 % with a partial current density of 27.9 mA cm−2 at − 0.9 V. • The catalyst exhibits ultra-long stability for more than 60 h. • The synergistic action of Pb SA and Cu atoms lowers the RDS for CO 2 RR to fromate. • Single-atom Pb induces Cu charge redistribution and inhibits the formation of COOH*. Exploring highly selective and stable electrocatalysts is of great significance for the electrochemical conversion of CO 2 into fuel. Herein, a three-dimensional (3D) nanostructure catalyst was developed by doping Pb single-atom (Pb SA) in-situ on carbon paper (Pb SA100 -Cu/CP) through a low-energy and economical method. The designed catalyst exhibited abundant active sites and was beneficial to CO 2 adsorption, activation, and subsequent conversion to fuel. Interestingly, Pb SA100 -Cu/CP showed a prominent Faraday efficiency (FE) of 97 % at –0.9 V versus reversible hydrogen electrode (vs. RHE) and a high partial current density of 27.9 mA·cm−2 for formate. Also, the catalyst remained significantly stable for 60 h during the durability test. The reaction mechanism was investigated by density functional theory (DFT), demonstrating that the doping Pb SA induced the electrons redistribution, promoted the formate generation, reduced the rate-determining step (RDS) energy barrier, and inhibited the hydrogen evolution reaction. The study aims to provide a new strategy for developing of single-atom catalysts with high selectivity and stability, which will help reduce environmental pressure and alleviate energy problems. [ABSTRACT FROM AUTHOR]

[Display omitted] • Mo, W doped Co 2 P/NF electrodes were designed for HER and GOR. • High catalytic efficiencies for HER, GOR were fulfilled. • The surface evolved CoO 2 was the genuine catalytic species for GOR. • H 2 and formate were coproduced by energy-saving glycerol electrolysis. H 2 and formate are important energy carriers in fuel-cells and feedstocks in chemical industry. The hydrogen evolution reaction (HER) coupling with electro-oxidative cleavage of thermodynamically favorable polyols is a promising way to coproduce H 2 and formate via electrochemical means, highly active catalysts for HER and electrooxidative cleavage of polycols are the key to achieve such a goal. Herein, molybdenum (Mo), tungsten (W) doped cobalt phosphides (Co 2 P) deposited onto nickel foam (NF) substrate, denoted as Mo-Co 2 P/NF and W-Co 2 P/NF, respectively, were investigated as catalytic electrodes for HER and electrochemical glycerol oxidation reaction (GOR) to yield H 2 and formate. The W-Co 2 P/NF electrode exhibited low overpotential (η) of 113 mV to attain a current density (J) of −100 mA cm−2 for HER, while the Mo-Co 2 P/NF electrode demonstrated high GOR efficiency for selective production of formate. In situ Raman and infrared spectroscopic characterizations revealed that the evolved CoO 2 from Co 2 P is the genuine catalytic sites for GOR. The asymmetric electrolyzer based on W-Co 2 P/NF cathode and Mo-Co 2 P/NF anode delivered a J = 100 mA cm−2 at 1.8 V voltage for glycerol electrolysis, which led to 18.2 % reduced electricity consumption relative to water electrolysis. This work highlights the potential of heteroelement doped phosphide in catalytic performances for HER and GOR, and opens up new avenue to coproduce more widespread commodity chemicals via gentle and sustainable electrocatalytic means. [ABSTRACT FROM AUTHOR]

Production of medium chain length polyhydroxyalkanoate (mcl-PHA) was attempted using Pseudomonas gessardii NIBRBAC000509957, which was isolated from Sunchang, Jeollabuk-do, Republic of Korea (35°24′27.7"N, 127°09′13.0"E) and effectively utilized acetate and formate as carbon sources. We first evaluated the utilization of acetate as a carbon source, revealing optimal growth at 5 g/L acetate. Then, formate was supplied to the acetate minimal medium as a carbon source to enhance cell growth. After overexpressing the acetate and formate assimilation pathway enzymes, this strain grew at a significantly higher rate in the medium. As this strain naturally produces PHA, it was further engineered metabolically to enhance mcl-PHA production. The engineered strain produced 0.40 g/L of mcl-PHA with a biomass content of 30.43% in fed-batch fermentation. Overall, this strain can be further developed to convert acetate and formate into valuable products. [ABSTRACT FROM AUTHOR]

Ever‐increasing emissions of anthropogenic carbon dioxide (CO2) cause global environmental and climate challenges. Inspired by biological photosynthesis, developing effective strategies NeuNlto up‐cycle CO2 into high‐value organics is crucial. Electrochemical CO2 reduction reaction (CO2RR) is highly promising to convert CO2 into economically viable carbon‐based chemicals or fuels under mild process conditions. Herein, mesoporous indium supported on multi‐walled carbon nanotubes (mp‐In@MWCNTs) is synthesized via a facile wet chemical method. The mp‐In@MWCNTs electrocatalysts exhibit high CO2RR performance in reducing CO2 into formate. An outstanding activity (current density −78.5 mA cm−2), high conversion efficiency (Faradaic efficiency of formate over 90%), and persistent stability (~30 h) for selective CO2‐to‐formate conversion are observed. The outstanding CO2RR process performance is attributed to the unique structures with mesoporous surfaces and a conductive network, which promote the adsorption and desorption of reactants and intermediates while improving electron transfer. These findings provide guiding principles for synthesizing conductive metal‐based electrocatalysts for high‐performance CO2 conversion. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction (ECO2RR) is capable of converting CO2 into a wide range of value‐added products under relatively mild conditions. Electrocatalyst with high selectivity and activity is crucial for high efficient ECO2RR. Herein, Bi‐In2O3 nanoflower catalysts with different metal ratios synthesized by wet chemical method are used for ECO2RR to produce formate. The results indicate that the hydrogen evolution activity of the Bi‐In2O3 catalysts during ECO2RR is suppressed at a low level and the activity and selectivity of formate production is related to the ratio of Bi to In content in the catalysts. The optimized Bi‐In2O3 catalyst with the ratio of Bi6In94 can achieve a high formate Faradaic efficiency (FEformate) over 80 % under a wide potential range from −0.7 V to −1.2 V vs. RHE, with the maximum value of 88.1 % at −0.7 V vs. RHE. Meanwhile, the highest formate partial current density reaches 47.7 mA cm−2 at −1.2 V vs. RHE and the current density and Faradaic efficiency remain stable during the 10 h stability test. The enhanced formate formation on Bi‐In2O3 NF can be attributed to the synergistic effect between Bi and In according to the characterizations of the Bi‐In2O3 NF. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction reaction (CO2RR) provides a promising way for producing value‐added fuels and chemicals via renewable electricity. However, the dynamic reconstruction of electrocatalysts of atomic active sites hinders in‐depth understanding of catalytic mechanism and further industrial application, especially under ampere‐level current density conditions. In this work, electro‐induced crystallization is reported over an amorphous Indium hydroxide gel (In gel) catalyst, which generates active sites for efficient and selective CO2RR. Molecular dynamic calculation reveals the crystallization process can maintain amorphous In‐OH species on the surface while generating crystallized metallic In under electroreduction condition; structural characterizations prove that the derived partially crystallized In gel is stable consisting of amorphous/crystalline interface, even biased at a high polarization potential of −4 V versus reversible hydrogen electrode. The resultant partially crystalized In gel exhibits a highly selective CO2RR performance toward formate under an ampere‐level current density up to 1200 mA cm−2 simultaneously with 91.89% Faradaic efficiency, which can motivate a high formate generation rate of 20.55 mmol h−1 cm−2. The operando Raman spectroscopic and density functional theoretic results demonstrate the optimized adsorption of *HCOO intermediate for the enhanced formate activity and selectivity over the partially crystallized In gel. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Herein, we report an efficient and practical protocol for the photoinduced dehalocyclization of ortho‐halophenylacrylamides with formate by the engagement of a CO2 radical anion to access substituted oxindoles. This method proceeds smoothly under mild conditions and exhibits a wide range of substrate as well as remarkable functional group compatibility. [ABSTRACT FROM AUTHOR]

Bi 2 O 3 catalyst with Bi-O bond crystal structure has more active sites, which shows better CO 2 catalytic performance than pure Bi catalysts in many catalytic reactions. How to strengthen the Bi-O bond in Bi 2 O 3 to obtain higher selectivity and catalytic activity is a problem worthy of consideration. Here, we develop a N 2 pre-reduced spherical Bi 2 O 3 /ATO catalyst that has a high formate Faradaic efficiency of 92.7%, which is superior to the existing tin oxide catalyst. Detailed electrocatalytic analysis shows that N 2 pre-reduction and spherical structure are helpful for Sn to stabilize the oxidation state of Bi, thus retaining part of the Bi-O structure. The existence of the Bi-O structure can reduce the energy barrier of the CO 2 production *OCHO reaction and promote the reaction rate of the CO 2 -*OCHO-HCOOH path, thus promoting the formation of formate. [ABSTRACT FROM AUTHOR]

Indium-based oxides are promising electrocatalysts for producing formate via CO2 reduction reaction, in which *OCHO is considered the key intermediate. Here, we identified that the *COOH pathway could be preferential to produce formate on In2O3 of In/In2O3 heterojunction due to the synergistic effect of oxygen species and vacancy. Specifically, *CO2 and *COOH were observed on In2O3 and related to formate production by in situ Raman spectroscopy. The theoretical calculations further demonstrated that the energy barrier of the *COOH formation on In2O3 was decreased in the presence of oxygen vacancy, similar to or lower than that of the *OCHO formation on the In surface. As a result, a formate selectivity of over 90% was obtained on prepared In/In2O3 heterojunction with 343 ± 7 mA cm-2 partial current density. Furthermore, when using a Si-based photovoltaic as an energy supplier, 10.11% solar--to--fuel energy efficiency was achieved. [ABSTRACT FROM AUTHOR]

Increasing atmospheric carbon dioxide levels, a reduction of arable land area and the dependence of first and second generation biotechnology feedstocks on agricultural products, call for alternative, sustainable feedstock sources for industrial applications. The direct use of CO2 or conversion of CO2 into other single carbon (C1) sources have great potential as they might help to reduce carbon emissions and do not compete with agricultural land use. Here we discuss the microbial use of C1 carbon sources, their potential applications in biotechnology, and challenges towards sustainable C1-based industrial biotechnology processes. We focus on methanol, formic acid, methane, syngas, and CO2 as feedstocks for bioprocesses, their assimilation pathways, current and emerging applications, and limitations of their application. This mini-review is intended as a first introduction for researchers who are new to the field of C1 biotechnology. [ABSTRACT FROM AUTHOR]

[Display omitted] • A Mn-doped nickel iron layered double hydroxides (Mn-doped NiFe-LDH) supported on nickel foam was developed, and could act as an efficient bifunctional catalyst for the coupling MOR and HER. • The methanol-to-formate faradaic efficiency was determined to be 99.5 % at an external potential of 1.5 V versus reversible hydrogen electrode. • This electrocatalyst is able to drive a current density of 131.1 mA cm−2 with a decay of merely 12.2 % over continuous 120 h testing in co-electrocatalysis of water/methanol solution. Electrochemical upgrading methanol into value-added formate at the anode in alkaline media enables the boosting production of hydrogen fuel at the cathode with saved energy. To achieve such a cost-effective and efficient electrocatalytic process, herein this work presents a Mn-doped nickel iron layered double hydroxides supported on nickel foam, derived from a simple hydrothermal synthesis. This developed electrocatalyst could act as an efficient bifunctional electrocatalyst for methanol-to-formate with a high faradaic efficiency of nearly 100 %, and for hydrogen evolution reaction, at an external potential of 1.5 V versus reversible hydrogen electrode. Additionally, a current density of 131.1 mA cm−2 with a decay of merely 12.2 % over 120 h continuous long-term testing was generated in co-electrocatalysis of water/methanol solution. Further density functional theoretical calculations were used to unravel the methanol-to-formate reaction mechanism arising from the doping of Fe and/or Mn. This work offers a good example of co-electrocatalysis to produce formate and green hydrogen fuel using a bifunctional electrocatalyst. [ABSTRACT FROM AUTHOR]

The escalating levels of atmospheric CO2, primarily attributed to human activities, underscore the urgent need for innovative solutions to mitigate environmental challenges. This study delves into the electrochemical reduction of CO2 as a promising avenue for sustainable carbon capture and utilization. Focused on the formation of formate (HCOO−/HCOOH), a high-value product, the research explores the integration of nonthermal plasma (NTP) with electrochemical processes—an approach rarely studied in existing literature. A comprehensive investigation involves varying parameters such as plasma discharging voltage, carrier gas, discharging mode, electrolysis voltage, polarity, and plasma type. The electrochemical tests employ a 10 wt.% Pd/C catalyst, and formate production is quantitatively analyzed using NMR. Results reveal that NTP significantly enhances CO2 reduction, with key factors influencing formate yield elucidated. The study reveals the complexity of CO2 electrochemical reduction, providing novel insights into the synergistic effects of NTP. These findings contribute to advancing sustainable technologies for CO2 utilization, paving the way for more efficient and environmentally friendly processes in the pursuit of a carbon-neutral future. [ABSTRACT FROM AUTHOR]

Abstract Electrolyte plays crucial roles in electrochemical CO2 reduction reaction (e‐CO2RR), yet how it affects the e‐CO2RR performance still being unclarified. In this work, it is reported that Sn‐Zn hybrid oxide enables excellent CO2‐to‐HCOO− conversion in KHCO3 with a HCOO− Faraday efficiency ≈89%, a yield rate ≈0.58 mmol cm−2 h−1 and a stability up to ≈60 h at −0.93 V, which are higher than those in NaHCO3 and K2SO4. Systematical characterizations unveil that the surface reconstruction on Sn‐Zn greatly depends on the electrolyte using: the Sn‐SnO2/ZnO, the ZnO encapsulated Sn‐SnO2/ZnO and the Sn‐SnO2/Zn‐ZnO are reconstructed on the surface by KHCO3, NaHCO3 and K2SO4, respectively. The improved CO2‐to‐HCOO− performance in KHCO3 is highly attributed to the reconstructed Sn‐SnO2/ZnO, which can enhance the charge transportation, promote the CO2 adsorption and optimize the adsorption configuration, accumulate the protons by enhancing water adsorption/cleavage and limit the hydrogen evolution. The findings may provide insightful understanding on the relationship between electrolyte and surface reconstruction in e‐CO2RR and guide the design of novel electrocatalyst for effective CO2 reduction.