Multicarbon Compounds Research Articles

Boosting CO2 Electroreduction to Multicarbon Products via Tuning of the Copper Surface Charge

Electrochemical CO2 reduction (ECR) to multicarbon compounds holds great potential but remains plagued with large overpotential, low Faradaic efficiency (FE), and debilitating competition from the evolution of hydrogen and the C1 product. The design and development of advanced catalytic systems is required to overcome these problems. Here, we demonstrate the selective cathodic CO2 conversion to C2+ chemicals (C2H4, C2H5OH, and n-C3H7OH) by optimizing the surface charge of Cu via fine-tuned annealing of CuSiO3@SiO2. Stabilization of Cu+ by forming Cu–O–Si bonds is attained, as predicted by density functional theory (DFT) calculations and evidenced by multiple experiments. The C2+ selectivity is readily regulated by adjusting the surface content of Cu+, underpinning its significance during the ECR. The resulting Cuδ+@SiO2 with a Cu0-to-Cu+ surface ratio of ∼0.5 achieves a remarkable C2+ FE as high as ∼70%, C2+ partial geometric current density of about 9 mA cm–2, and large C2+-to-C1 ratio of ∼10, using an H-type cell in aqueous CsBr electrolytes at mild overpotentials. The high C2+ FE and current density persist over 12 h of continuous CO2 electrolysis. In addition, a respectable C2+ FE of ∼52% can still be attained even at a large current density (500 mA cm–2) in a flow reactor system. DFT computations reveal that the oxidized copper species Cu+ boosts C–C coupling by lessening the formation energy of the critical *OCCOH intermediate. This work underscores the prominent role of the support–catalyst interaction and the modulation of Cu oxidation states in steering the ECR selectivity.

Three multi-enzyme cascade pathways for conversion of C1 to C2/C4 compounds

A feasible and promising carbon reduction strategy is to convert CO 2 into C1 compounds through renewable energy-driven first and then use a multi-enzyme cascade to obtain compounds with higher carbon numbers and market value. In this study, three multi-enzyme cascade pathways for preparing important C2/C4 compounds (ethylene glycol [EG], glycolic acid [GA], and d -erythrose) from methanol were proposed. All pathways use glycolaldehyde as the key intermediate, which can be obtained from methanol through glycolaldehyde synthase and alcohol oxidase cascade. Then, the target compounds can be acquired by adding different enzymes. As a result, 0.90 g/L EG, 0.33 g/L GA, and 53.65 mg/L d -erythrose were produced from methanol. Compared with the titers of EG (6.6 mM) and GA (1.2 g/L) synthesis routes from formaldehyde reported in the literature, the titers of this study (27.58 mM EG and 1.59 g/L GA from formaldehyde) were significantly improved. • Glycolic acid and d -erythrose pathways from CH 3 OH were proposed for the first time • DERA were found to have the function of condensing glycolaldehyde to d -erythrose • GOX were used to synthesize ethylene glycol from glycolaldehyde • ALDH were used to oxidize glycolaldehyde to glycolic acid Under the background of CO 2 is one of the main gases leading to the greenhouse effect and the inexpensive and widespread feedstock. Coupling the renewable energy-driven CO 2 capture technology with multi-enzyme cascade catalytic conversion of C1 compounds to multi-carbon compounds is a promising method for CO 2 utilization. In this case, we successfully constructed three multi-enzyme cascade pathways to synthesize important C2/C4 compounds (ethylene glycol, glycolic acid, and d -erythrose) from C1 compounds. The pathways proposed herein could contribute to realizing the recycling of carbon resources and solving the problems of plastic pollution and energy shortage. They could also provide a new impetus for the design of chemo-bio routes for the efficient conversion of CO 2 into compounds with higher carbon numbers and market value. Junhui et al. successfully constructed three multi-enzyme pathways for synthesizing C2/C4 compounds (ethylene glycol, glycolic acid, and d -erythrose) from C1 compounds. Glycolic acid or d -erythrose pathways were proposed for the first time. Three new kinds of enzymes were found to catalyze intermediate glycolaldehyde to synthesize such C2/C4 compounds.

Creation of SnxNb1−xO2 solid solution through heavy Nb-doping in SnO2 to boost its photocatalytic CO2 reduction to C2+ products under simulated solar illumination

Photocatalytic CO2 reduction driven by green solar energy could be a promising approach for the carbon neutral practice. In this work, a novel defect engineering approach was developed to form the SnxNb1−xO2 solid solution by the heavy substitutional Nb-doping of SnO2 through a robust hydrothermal process. The detailed analysis demonstrated that the heavy substitution of Sn4+ by a higher valence Nb5+ created a more suitable band structure, a better photogenerated charge carrier separation and transfer, and stronger CO2 adsorption due to the presence of abundant acid centers and excess electrons on its surface. Thus, the SnxNb1−xO2 solid solution sample demonstrated a much better photocatalytic CO2 reduction performance compared to the pristine SnO2 sample without the need for sacrificial agent. Its photocatalytic CO2 reduction efficiency reached ∼292.47 µmol/(g·h), which was 19 times that of the pristine SnO2 sample. Furthermore, its main photocatalytic CO2 reduction product was a more preferred multi-carbon (C2+) compound of C2H5OH, while that of the pristine SnO2 sample was a one-carbon (C1) compound of CH3OH. This work demonstrated that, the heavy doping of high valence cations in metal oxides to form solid solution may enhance the photocatalytic CO2 reduction and modulate its reduction process, to produce more C2+ products. This material design strategy could be readily applied to various material systems for the exploration of high-performance photocatalysts for the solar-driven CO2 reduction.

Molecular Catalysts for the Reductive Homocoupling of CO2 towards C2+ Compounds.

The conversion of CO2 into multicarbon (C2+) compounds by reductive homocoupling offers the possibility to transform renewable energy into chemical energy carriers and thereby create “carbon‐neutral” fuels or other valuable products. Most available studies have employed heterogeneous metallic catalysts, but the use of molecular catalysts is still underexplored. However, several studies have already demonstrated the great potential of the molecular approach, namely, the possibility to gain a deep mechanistic understanding and a more precise control of the product selectivity. This Minireview summarizes recent progress in both the thermo‐ and electrochemical reductive homocoupling of CO2 toward C2+ products mediated by molecular catalysts. In addition, reductive CO homocoupling is discussed as a model for the further conversion of intermediates obtained from CO2 reduction, which may serve as a source of inspiration for developing novel molecular catalysts in the future.

Molecular Catalysts for the Reductive Homocoupling of CO2 towards C2+ Compounds

AbstractThe conversion of CO2 into multicarbon (C2+) compounds by reductive homocoupling offers the possibility to transform renewable energy into chemical energy carriers and thereby create “carbon‐neutral” fuels or other valuable products. Most available studies have employed heterogeneous metallic catalysts, but the use of molecular catalysts is still underexplored. However, several studies have already demonstrated the great potential of the molecular approach, namely, the possibility to gain a deep mechanistic understanding and a more precise control of the product selectivity. This Minireview summarizes recent progress in both the thermo‐ and electrochemical reductive homocoupling of CO2 toward C2+ products mediated by molecular catalysts. In addition, reductive CO homocoupling is discussed as a model for the further conversion of intermediates obtained from CO2 reduction, which may serve as a source of inspiration for developing novel molecular catalysts in the future.

Unravelling Formaldehyde Metabolism in Bacteria: Road towards Synthetic Methylotrophy.

Formaldehyde metabolism is prevalent in all organisms, where the accumulation of formaldehyde can be prevented through the activity of dissimilation pathways. Furthermore, formaldehyde assimilatory pathways play a fundamental role in many methylotrophs, which are microorganisms able to build biomass and obtain energy from single- and multicarbon compounds with no carbon–carbon bonds. Here, we describe how formaldehyde is formed in the environment, the mechanisms of its toxicity to the cells, and the cell’s strategies to circumvent it. While their importance is unquestionable for cell survival in formaldehyde rich environments, we present examples of how the modification of native formaldehyde dissimilation pathways in nonmethylotrophic bacteria can be applied to redirect carbon flux toward heterologous, synthetic formaldehyde assimilation pathways introduced into their metabolism. Attempts to engineer methylotrophy into nonmethylotrophic hosts have gained interest in the past decade, with only limited successes leading to the creation of autonomous synthetic methylotrophy. Here, we discuss how native formaldehyde assimilation pathways can additionally be employed as a premise to achieving synthetic methylotrophy. Lastly, we discuss how emerging knowledge on regulation of formaldehyde metabolism can contribute to creating synthetic regulatory circuits applied in metabolic engineering strategies.

Highly selective synthesis of multicarbon compounds by carbon dioxide hydrogenation over Pt nanocrystals anchoring Ru clusters

Carbon supported Pt nanocrystals anchoring small Ru nanoclusters (Ru-co-Pt/C) could catalyze CO2 hydrogenation to form multi-carbon compounds (C2–C26) with an extraordinary C2+ selectivity of 90.1% at 130 °C.

Insight into Composition and Intermediate Evolutions of Copper-Based Catalysts during Gas-Phase CO2 Electroreduction to Multicarbon Oxygenates

Conversion of CO2 to valuable chemicals driven by renewable electricity via electrocatalytic reduction processes is of great significance for achieving carbon neutrality. Copper-based materials distinguish themselves from other electrocatalysts for their unique capability to produce multicarbon compounds in CO2 electroreduction. However, the intrinsic active composition and C–C coupling mechanism of copper-based catalysts are still ambiguous. This is largely due to the absence of appropriate in situ approaches to monitor the complicated processes of CO2 electroreduction. Here, we adopted operando spectroscopy techniques, including Raman and infrared, to investigate the evolution of compositions and intermediates during gas-phase CO2 electroreduction on Cu foam, Cu2O nanowire and CuO nanowire catalysts. Although all the three copper-based catalysts possessed the activity of electroreducing gas-phase CO2 to multicarbon oxygenates, Cu2O nanowires showed the much superior performance with a 71.9% Faradaic efficiency of acetaldehyde. Operando Raman spectra manifested that the cuprous oxide remained stable during the whole gas-phase CO2 electroreduction, and operando diffuse reflectance infrared Fourier transform spectroscopy (DRFITS) results provide direct evidences of key intermediates and their evolutions for producing multicarbon oxygenates, in consistence with the density functional theory calculations.

Conversion of CO2 to Multi-carbon Compounds over a CoCO3 Supported Ru-Pt Catalyst Under Mild Conditions

Conversion of CO2 to Multi-carbon Compounds over a CoCO3 Supported Ru-Pt Catalyst Under Mild Conditions

Genome-Scale Analysis of Acetobacterium woodii Identifies Translational Regulation of Acetogenesis.

ABSTRACTAcetogens synthesize acetyl-CoA via the CO2-fixing Wood-Ljungdahl pathway. Despite their ecological and biotechnological importance, their translational regulation of carbon and energy metabolisms remains unclear. Here, we report how carbon and energy metabolisms in the model acetogen Acetobacterium woodii are translationally controlled under different growth conditions. Data integration of genome-scale transcriptomic and translatomic analyses revealed that the acetogenesis genes, including those of the Wood-Ljungdahl pathway and energy metabolism, showed changes in translational efficiency under autotrophic growth conditions. In particular, genes encoding the Wood-Ljungdahl pathway are translated at similar levels to achieve efficient acetogenesis activity under autotrophic growth conditions, whereas genes encoding the carbonyl branch present increased translation levels in comparison to those for the methyl branch under heterotrophic growth conditions. The translation efficiency of genes in the pathways is differentially regulated by 5′ untranslated regions and ribosome-binding sequences under different growth conditions. Our findings provide potential strategies to optimize the metabolism of syngas-fermenting acetogenic bacteria for better productivity.IMPORTANCE Acetogens are capable of reducing CO2 to multicarbon compounds (e.g., ethanol or 2,3-butanediol) via the Wood-Ljungdahl pathway. Given that protein synthesis in bacteria is highly energy consuming, acetogens living at the thermodynamic limit of life are inevitably under translation control. Here, we dissect the translational regulation of carbon and energy metabolisms in the model acetogen Acetobacterium woodii under heterotrophic and autotrophic growth conditions. The latter may be experienced when acetogen is used as a cell factory that synthesizes products from CO2 during the gas fermentation process. We found that the methyl and carbonyl branches of the Wood-Ljungdahl pathway are activated at similar translation levels during autotrophic growth. Translation is mainly regulated by the 5′-untranslated-region structure and ribosome-binding-site sequence. This work reveals novel translational regulation for coping with autotrophic growth conditions and provides the systematic data set, including the transcriptome, translatome, and promoter/5′-untranslated-region bioparts.

One Nanometer PtIr Nanowires as High-Efficiency Bifunctional Catalysts for Electrosynthesis of Ethanol into High Value-Added Multicarbon Compound Coupled with Hydrogen Production.

The electrosynthesis of high-value-added multicarbon compounds coupled with hydrogen production is an efficient way to achieve carbon neutrality; however, the lack of effective bifunctional catalysts in electrosynthesis largely hinders its development. Herein, we report the first example on the highly efficient electrosynthesis of high-value-added 1,1-diethoxyethane (DEE) at the anode and high-purity hydrogen at the cathode using 1 nm PtIr nanowires (NWs) as the bifunctional catalysts. We demonstrate that the cell using 1 nm PtIr nanowires as the bifunctional catalysts can achieve a reported lowest voltage of 0.61 V to reach the current density of 10 mA cm-2, much lower than those of the Pt NWs (0.85 V) and commercial Pt/C (0.86 V), and also can have the highest Faraday efficiencies of 85% for DEE production and 94.0% for hydrogen evolution in all the reported electrosynthesis catalysts. The in situ infrared spectroscopy study reveals that PtIr NWs can facilitate the activation of O-H and C-H bonds in ethanol, which is important for the formation of acetaldehyde intermediate, and finally DEE. In addition, the cell using PtIr NWs as bifunctional catalysts exhibits excellent stability by showing almost no obvious decrease in the Faraday efficiency of the DEE production.

Inside Cover: A Modular In Vitro Platform for the Production of Terpenes and Polyketides from CO2 (Angew. Chem. Int. Ed. 30/2021)

Direct conversion of the greenhouse gas CO2 into value-added compounds remains a major challenge. Simultaneous one-pot coupling of a synthetic CO2-fixing cycle with a natural glyoxylate assimilation module and different natural product biosynthetic pathways enables the production of valuable terpenes and polyketides directly from CO2. Demonstration of this modular in vitro platform sets the stage for harnessing the greenhouse gas CO2 as source for the sustainable synthesis of multi-carbon compounds, as reported by Tobias J. Erb et al. in their Communication on page 16420.

A rich catalog of C\u2013C bonded species formed in CO2 reduction on a plasmonic photocatalyst

The understanding and rational design of heterogeneous catalysts for complex reactions, such as CO2 reduction, requires knowledge of elementary steps and chemical species prevalent on the catalyst surface under operating conditions. Using in situ nanoscale surface-enhanced Raman scattering, we probe the surface of a Ag nanoparticle during plasmon-excitation-driven CO2 reduction in water. Enabled by the high spatiotemporal resolution and surface sensitivity of our method, we detect a rich array of C1–C4 species formed on the photocatalytically active surface. The abundance of multi-carbon compounds, such as butanol, suggests the favorability of kinetically challenging C–C coupling on the photoexcited Ag surface. Another advance of this work is the use of isotope labeling in nanoscale probing, which allows confirmation that detected species are the intermediates and products of the catalytic reaction rather than spurious contaminants. The surface chemical knowledge made accessible by our approach will inform the modeling and engineering of catalysts.

The one-pot synthesis of a ZnSe/ZnS photocatalyst for H2 evolution and microbial bioproduction

Low-cost photocatalysts are being developed for the conversion of visible light into H2 and to drive CO2 reduction. Hybrid photosynthesis is a promising approach to convert CO2 and visible light into multicarbon compounds where a photocatalyst energizes the metabolism of an autotrophic microbe. Here, a heterostructure ZnSe/ZnS photocatalyst was synthesized by a simple one-pot method and evaluated for photocatalytic H2 evolution (PHE) as well as for hybrid photosynthesis with the bioplastic-producing bacterium Ralstonia eutropha. ZnSe/ZnS nanoparticles exhibited a PHE 5.5 times higher than pure ZnSe. Photoluminescence and photoelectrochemical characterization of ZnSe/ZnS demonstrated more efficient charge separation probably caused by ZnS defects. Furthermore, ZnSe/ZnS improved 1.3 times bioplastic production from CO2 by R. eutropha, which was not the case for pure ZnSe. These results show ZnSe/ZnS potential for both PHE as well as hybrid photosynthesis and provide insights on the photocatalytic reaction mechanisms involved when the two Zn-based materials are combined.

Hierarchical Copper with Inherent Hydrophobicity Mitigates Electrode Flooding for High-Rate CO2 Electroreduction to Multicarbon Products.

Copper is currently the material with the most promise as catalyst to drive carbon dioxide (CO2) electroreduction to produce value-added multicarbon (C2+) compounds. However, a copper catalyst on a carbon-based gas diffusion layer electrode often has poor stability-especially when performing at high current densities-owing to electrolyte flooding caused by the hydrophobicity decrease of the gas diffusion layer during operation. Here, we report a bioinspired copper catalyst on a gas diffusion layer that mimics the unique hierarchical structuring of Setaria's hydrophobic leaves. This hierarchical copper structure endows the CO2 reduction electrode with sufficient hydrophobicity to build a robust gas-liquid-solid triple-phase boundary, which can not only trap more CO2 close to the active copper surface but also effectively resist electrolyte flooding even under high-rate operation. We consequently achieved a high C2+ production rate of 255 ± 5.7 mA cm-2 with a 64 ± 1.4% faradaic efficiency, as well as outstanding operational stability at 300 mA cm-2 over 45 h in a flow reactor, largely outperforming its wettable copper counterparts.

A Novel Moderately Thermophilic Facultative Methylotroph within the Class Alphaproteobacteria.

Methylotrophic bacteria (non-methanotrophic methanol oxidizers) consuming reduced carbon compounds containing no carbon–carbon bonds as their sole carbon and energy source have been found in a great variety of environments. Here, we report a unique moderately thermophilic methanol-oxidising bacterium (strain LS7-MT) that grows optimally at 55 °C (with a growth range spanning 30 to 60 °C). The pure isolate was recovered from a methane-utilizing mixed culture enrichment from an alkaline thermal spring in the Ethiopia Rift Valley, and utilized methanol, methylamine, glucose and a variety of multi-carbon compounds. Phylogenetic analysis of the 16S rRNA gene sequences demonstrated that strain LS7-MT represented a new facultatively methylotrophic bacterium within the order Hyphomicrobiales of the class Alphaproteobacteria. This new strain showed 94 to 96% 16S rRNA gene identity to the two methylotroph genera, Methyloceanibacter and Methyloligella. Analysis of the draft genome of strain LS7-MT revealed genes for methanol dehydrogenase, essential for methanol oxidation. Functional and comparative genomics of this new isolate revealed genomic and physiological divergence from extant methylotrophs. Strain LS7-MT contained a complete mxaF gene cluster and xoxF1 encoding the lanthanide-dependent methanol dehydrogenase (XoxF). This is the first report of methanol oxidation at 55 °C by a moderately thermophilic bacterium within the class Alphaproteobacteria. These findings expand our knowledge of methylotrophy by the phylum Proteobacteria in thermal ecosystems and their contribution to global carbon and nitrogen cycles.

Partially reduced Pd single atoms on CdS nanorods enable photocatalytic reforming of ethanol into high value-added multicarbon compound

<h2>Summary</h2> Photocatalytic co-production of high value-added multicarbon compounds and hydrogen from renewable bioethanol is an environmental and long-term approach to industrial activities and remains a great challenge because of the difficulty in bioethanol dehydrogenation. Guided by first-principle simulation, we first synthesized a partially reduced Pd–P₃ single atom (PdPSA) on CdS nanorods with an unoccupied hybrid state of Pd 4d and P 3p via both metal-support interaction effect and Pd–P coordination effect. This unique electronic structure of PdPSA is totally different from highly reduced S-coordinated Pd single atoms or nanoparticles and allows PdPSA-CdS to exhibit a visible-light photocatalytic activity of 35.1 mmol g⁻¹ h⁻¹ for the co-production of high-value-added 1,1-diethoxyethane and H₂ with a selectivity of 100%. Mechanism studies revealed that the unoccupied hybrid states of Pd 4d and P 3p in PdPSA not only greatly promoted the dehydrogenation of ethanol but also promised PdPSA with a high H₂-production activity.

Isolated copper single sites for high-performance electroreduction of carbon monoxide to multicarbon products

Electrochemical carbon monoxide reduction is a promising strategy for the production of value-added multicarbon compounds, albeit yielding diverse products with low selectivities and Faradaic efficiencies. Here, copper single atoms anchored to Ti3C2Tx MXene nanosheets are firstly demonstrated as effective and robust catalysts for electrochemical carbon monoxide reduction, achieving an ultrahigh selectivity of 98% for the formation of multicarbon products. Particularly, it exhibits a high Faradaic efficiency of 71% towards ethylene at −0.7 V versus the reversible hydrogen electrode, superior to the previously reported copper-based catalysts. Besides, it shows a stable activity during the 68-h electrolysis. Theoretical simulations reveal that atomically dispersed Cu–O3 sites favor the C–C coupling of carbon monoxide molecules to generate the key *CO-CHO species, and then induce the decreased free energy barrier of the potential-determining step, thus accounting for the high activity and selectivity of copper single atoms for carbon monoxide reduction.

Electrocatalytic reduction of CO2 and CO to multi-carbon compounds over Cu-based catalysts.

The electrocatalytic reduction of CO2 with H2O to multi-carbon (C2+) compounds, in particular, C2+ olefins and oxygenates, which have versatile applications in the chemical and energy industries, holds great potential to mitigate the depletion of fossil resources and abate carbon emissions. There are two major routes for the electrocatalytic CO2 reduction to C2+ compounds, i.e., the direct route and the indirect route via CO. The electrocatalytic CO2 reduction to CO has been commercialised with solid oxide electrolysers, making the indirect route via CO to C2+ compounds also a promising alternative. This tutorial review focuses on the similarities and differences in the electrocatalytic CO2 and CO reduction reactions (CO2RR and CORR) into C2+ compounds, including C2H4, C2H5OH, CH3COO- and n-C3H7OH, over Cu-based catalysts. First, we introduce the fundamental aspects of the two electrocatalytic reactions, including the cathode and anode reactions, electrocatalytic reactors and crucial performance parameters. Next, the reaction mechanisms, in particular, the C-C coupling mechanism, are discussed. Then, efficient catalysts and systems for these two reactions are critically reviewed. We analyse the key factors that determine the selectivity, activity and stability for the electrocatalytic CO2RR and CORR. Finally, the opportunities, challenges and future trends in the electrocatalytic CO2RR and CORR are proposed. These insights will offer guidance for the design of industrial-relevant catalysts and systems for the synthesis of C2+ olefins and oxygenates.

Pd-Modified ZnO-Au Enabling Alkoxy Intermediates Formation and Dehydrogenation for Photocatalytic Conversion of Methane to Ethylene.

Photocatalysis provides an intriguing approach for the conversion of methane to multicarbon (C2+) compounds under mild conditions; however, with methyl radicals as the sole reaction intermediate, the current C2+ products are dominated by ethane, with a negligible selectivity toward ethylene, which, as a key chemical feedstock, possesses higher added value than ethane. Herein, we report a direct photocatalytic methane-to-ethylene conversion pathway involving the formation and dehydrogenation of alkoxy (i.e., methoxy and ethoxy) intermediates over a Pd-modified ZnO-Au hybrid catalyst. On the basis of various in situ characterizations, it is revealed that the Pd-induced dehydrogenation capability of the catalyst holds the key to turning on the pathway. During the reaction, methane molecules are first dissociated into methoxy on the surface of ZnO under the assistance of Pd. Then these methoxy intermediates are further dehydrogenated and coupled with methyl radical into ethoxy, which can be subsequently converted into ethylene through dehydrogenation. As a result, the optimized ZnO-AuPd hybrid with atomically dispersed Pd sites in the Au lattice achieves a methane conversion of 536.0 μmol g-1 with a C2+ compound selectivity of 96.0% (39.7% C2H4 and 54.9% C2H6 in total produced C2+ compounds) after 8 h of light irradiation. This work provides fresh insight into the methane conversion pathway under mild conditions and highlights the significance of dehydrogenation for enhanced photocatalytic activity and unsaturated hydrocarbon product selectivity.