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

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

Engineering Surface Amine Modifiers of Ultrasmall Gold Nanoparticles Supported on Reduced Graphene Oxide for Improved Electrochemical CO2 Reduction

Ultrasmall gold (Au) nanoparticles with high mass activity have great potential for practical applications in CO₂ electroreduction. However, these nanoparticles often suffer from poor product selectivity since their abundant low‐coordinated sites are favorable for H₂ evolution. In this work, a catalyst, reduced graphene oxide supported ultrasmall Au nanoparticles (≈2.4 nm) is developed which delivers high Au‐specific mass activities (>100 A g^?1) and good Faradaic efficiencies (32–60%) for the CO₂‐to‐CO conversion at moderate overpotentials (450–600 mV). The efficiencies can be improved to 59–75% while retaining the ultrahigh mass activities via a simple amine‐modification strategy. In addition, an amine‐structure‐dependent effect is revealed: linear amines promote the CO formation whereas the branched polyamine greatly depresses it; the increasing alkyl chain length boosts the promotion effect of linear amines. The strong Au‐amine interaction and molecular configuration induced amine coverage on the ultrasmall Au NPs may contribute to this effect.     

Atomic‐Level Reactive Sites for Semiconductor‐Based Photocatalytic CO2 Reduction

Photocatalytic CO₂ reduction is an effective means to generate renewable energy. It involves redox reactions, reduction of CO₂ and oxidation of water, that leads to the production of solar fuel. Significant research effort has therefore been made to develop inexpensive and practically sustainable semiconductor‐based photocatalysts. The exploration of atomic‐level active sites on the surface of semiconductors can result in an improved understanding of the mechanism of CO₂ photoreduction. This can be applied to the design and synthesis of efficient photocatalysts. In this review, atomic‐level reactive sites are classified into four types: vacancies, single atoms, surface functional groups, and frustrated Lewis pairs (FLPs). These different photocatalytic reactive sites are shown to have varied affinity to reactants, intermediates, and products. This changes pathways for CO₂ reduction and significantly impacts catalytic activity and selectivity. The design of a photocatalyst from an atomic‐level perspective can therefore be used to maximize atomic utilization efficiency and lead to a high selectivity. The prospects for fabrication of effective photocatalysts based on an in‐depth understanding are highlighted.     

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

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

NiCoFe‐Layered Double Hydroxides/N‐Doped Graphene Oxide Array Colloid Composite as an Efficient Bifunctional Catalyst for Oxygen Electrocatalytic Reactions

Ternary NiCoFe‐layered double hydroxide (NiCo^IIIFe‐LDH) with Co³⁺ is grafted on nitrogen‐doped graphene oxide (N‐GO) by an in situ growth route. The array‐like colloid composite of NiCo^IIIFe‐LDH/N‐GO is used as a bifunctional catalyst for both oxygen evolution/reduction reactions (OER/ORR). The NiCo^IIIFe‐LDH/N‐GO array has a 3D open structure with less stacking of LDHs and an enlarged specific surface area. The hierarchical structure design and novel material chemistry endow high activity propelling O₂ redox. By exposing more amounts of Ni and Fe active sites, the NiCo^IIIFe‐LDH/N‐GO illustrates a relatively low onset potential (1.41 V vs reversible hydrogen electrode) in 0.1 mol L^?1 KOH solution under the OER process. Furthermore, by introducing high valence Co³⁺, the onset potential of this material in ORR is 0.88 V. The overvoltage difference is 0.769 V between OER and ORR. The key factors for the excellent bifunctional catalytic performance are believed to be the Co with a high valence, the N‐doping of graphene materials, and the highly exposed Ni and Fe active sites in the array‐like colloid composite. This work further demonstrates the possibility to exploit the application potential of LDHs as OER and ORR bifunctional electrochemical catalysts.     

Electrochemical CO2 Reduction with Atomic Iron‐Dispersed on Nitrogen‐Doped Graphene

Electrochemical reduction of CO₂ provides an opportunity to reach a carbon‐neutral energy recycling regime, in which CO₂ emissions from fuel use are collected and converted back to fuels. The reduction of CO₂ to CO is the first step toward the synthesis of more complex carbon‐based fuels and chemicals. Therefore, understanding this step is crucial for the development of high‐performance electrocatalyst for CO₂ conversion to higher order products such as hydrocarbons. Here, atomic iron dispersed on nitrogen‐doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO₂ reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen‐confined atomic Fe moieties on the nitrogen‐doped graphene layer is confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. The CO₂ reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N₄) embedded in nitrogen‐doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.     

Paramelaconite‐Enriched Copper‐Based Material as an Efficient and Robust Catalyst for Electrochemical Carbon Dioxide Reduction

A copper‐oxide‐based catalyst enriched with paramelaconite (Cu₄O₃) is presented and investigated as an electrocatalyst for facilitating electroreduction of CO₂ to ethylene and other hydrocarbons. Cu₄O₃ is a member of the copper‐oxide family and possesses an intriguing mixed‐valance nature, incorporating an equal number of Cu⁺ and Cu²⁺ ions in its crystal structure. The material is synthesized using a solvothermal synthesis route and its structure is confirmed via powder X‐ray diffraction, transmission electron microscope based selected area electron diffraction, and X‐ray photoelectron spectroscopy. A flow reactor equipped with a gas diffusion electrode is utilized to test a copper‐based catalyst enriched with the Cu₄O₃ phase under CO₂ reduction conditions. The Cu₄O₃‐rich catalyst (PrC) shows a Faradaic efficiency for ethylene over 40% at 400 mA cm^?2. At ?0.64 versus reversible hydrogen electrode, the highest C₂₊/C₁ product ratio of 4.8 is achieved, with C₂₊ Faradaic efficiency over 61%. Additionally, the catalyst exhibits a stable performance for 24 h at a constant current density of 200 mA cm^?2.     

Intermediates Adsorption Engineering of CO2 Electroreduction Reaction in Highly Selective Heterostructure Cu‐Based Electrocatalysts for CO Production

The challenge in the artificial CO₂ reduction to fuel is achieving high selective electrocatalysts. Here, a highly selective Cu₂O/CuO heterostructure electrocatalyst is developed for CO₂ electroreduction. The Cu₂O/CuO nanowires modified by Ni nanoparticles exhibit superior catalytic performance with high faradic efficiency (95% for CO). Theoretical and experimental analyses show that the hybridization of Cu₂O/CuO nanowires and Ni nanoparticles can not only adjust the d‐band center of electrocatalysts to enhance the intrinsic catalytic activity but also improve the adsorption of COOH* intermediates and suppress the hydrogen evolution reaction to promote the CO conversion efficiency during CO₂ reduction reaction. An in situ Raman spectroscopic study further confirms the existence of COOH* species and the engineering intermediates adsorption. This work offers new insights for facile designing of nonprecious transition metal compound heterostructure for CO₂ reduction reaction through adjusting the reaction pathway.     

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO2 to Value‐Added Chemicals and Fuel

Renewable‐electricity‐powered electrocatalytic CO₂ reduction reactions (CO₂RR) have been identified as an emerging technology to address the issue of rising CO₂ emissions in the atmosphere. While the CO₂RR has been demonstrated to be technically feasible, further improvements in catalyst performance through active sites engineering are a prerequisite to accelerate its commercial feasibility for utilization in large CO₂‐emitting industrial sources. Over the years, the improved understanding of the interaction of CO₂ with the active sites has allowed superior catalyst design and subsequent attainment of prominent CO₂RR activity in literature. This review tracks the evolution of the understanding of CO₂RR active sites on different electrocatalysts such as metals, metal‐oxides, single atoms, metal‐carbon, and subsequently metal‐free carbon‐based catalysts. Despite the tremendous research efforts in the field, many scientific questions on the role of various active sites in governing CO₂RR activity, selectivity, stability, and pathways are still unanswered. These gaps in knowledge are highlighted and a discussion is set forth on the merits of utilizing advanced in‐situ and operando characterization techniques and machine learning (ML). Using this technique, the underlying mechanisms can be discerned, and as a result new strategies for designing active sites may be uncovered. Finally, this review advocates an interdisciplinary approach to discover and design CO₂RR active sites (rather than focusing merely on catalyst activity) in a bid to stimulate practical research for industrial application.     

Revealing Pseudocapacitive Mechanisms of Metal Dichalcogenide SnS2/Graphene‐CNT Aerogels for High‐Energy Na Hybrid Capacitors

SnS₂ nanoplatelet electrodes can offer an exceptionally high pseudocapacitance in an organic Na⁺ ion electrolyte system, but their underlying mechanisms are still largely unexplored, hindering the practical applications of pseudocapacitive SnS₂ anodes in Na‐ion batteries (SIBs) and Na hybrid capacitors (SHCs). Herein, SnS₂ nanoplatelets are grown directly on SnO₂/C composites to synthesize SnS₂/graphene‐carbon nanotube aerogel (SnS₂/GCA) by pressurized sulfidation where the original morphology of carbon framework is preserved. The composite electrode possessing a large surface area delivers a remarkable specific capacity of 600.3 mA h g^?1 at 0.2 A g^?1 and 304.8 mA h g^?1 at an ultrahigh current density of 10 A g^?1 in SIBs. SHCs comprising a SnS₂/GCA composite anode and an activated carbon cathode present exceptional energy densities of 108.3 and 26.9 W h kg^?1 at power densities of 130 and 6053 W kg^?1, respectively. The in situ transmission electron microscopy and the density functional theory calculations reveal that the excellent pseudocapacitance originates from the combination of Na adsorption on the surface/Sn edge of SnS₂ nanoplatelets and ultrafast Na⁺ ion intercalation into the SnS₂ layers.     

Surface‐Plasmon‐Assisted Photoelectrochemical Reduction of CO2 and NO3− on Nanostructured Silver Electrodes

Electrochemical reduction of carbon dioxide (CO₂) typically suffers from low selectivity and poor reaction rates that necessitate high overpotentials, which impede its possible application for CO₂ capture, sequestration, or carbon‐based fuel production. New strategies to address these issues include the utilization of photoexcited charge carriers to overcome activation barriers for reactions that produce desirable products. This study demonstrates surface‐plasmon‐enhanced photoelectrochemical reduction of CO₂ and nitrate (NO₃^?) on silver nanostructured electrodes. The observed photocurrent likely originates from a resonant charge transfer between the photogenerated plasmonic hot electrons and the lowest unoccupied molecular orbital (MO) acceptor energy levels of adsorbed CO₂, NO₃^?, or their reductive intermediates. The observed differences in the resonant effects at the Ag electrode with respect to electrode potential and photon energy for CO₂ versus NO₃^? reduction suggest that plasmonic hot‐carriers interact selectively with specific MO acceptor energy levels of adsorbed surface species such as CO₂, NO₃^?, or their reductive intermediates. This unique plasmon‐assisted charge generation and transfer mechanism can be used to increase yield, efficiency, and selectivity of various photoelectrochemical processes.     

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

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

Carbon Solving Carbon's Problems: Recent Progress of Nanostructured Carbon‐Based Catalysts for the Electrochemical Reduction of CO2

The electrochemical reduction of CO₂ to useful molecules offers an elegant technological solution to current energy security and sustainability issues because it sequesters carbon from the atmosphere, provides an energy storage solution for intermittent renewable sources, and can be used to produce fuels and industrial chemicals. Nanostructured carbon materials have been extensively used to catalyse some key electrochemical processes because of their excellent electrical conductivity, chemical stability, and abundant active sites. This progress report focuses on nanostructured carbon materials, namely graphene materials, carbon nanotubes, porphyrin materials, nanodiamond, and glassy carbon, which have recently shown promise as high performing CO₂ reduction electrocatalysts and supports. Along with discussion regarding materials synthesis, structural characterisation, and electrochemical performance characterisation techniques used, this report will discuss the findings of recent computational CO₂RR studies which have been key to elucidating active sites and reaction mechanisms, and developing strategies to break conventional scaling relationships. Lastly, challenges and future perspective of these carbon‐based materials for CO₂ reduction applications will be given. Much work is still required to realise the commercial viability of the technology, but advanced experimental techniques coupled with theoretical calculations are expected to facilitate future development of the technology.     

A Simple Chiral Cu(II) Complex as an Effective Phase‐Transfer Catalyst for the Enantioselective Alkylation of Dissymmetric Glycinate Ketimines

Catalytic asymmetric benzylation of a dissymmetric tert‐butylglycinate ketimine, incorporating 1‐naphthyl and phenyl groups as the Schiff base substituents, under phase‐transfer conditions was investigated. It was interesting to note that the sense of asymmetric induction of the alkylation of Z‐imine stereoisomer is opposite to that of the corresponding E stereoisomer with a similar degree of enantioselectivity. More interestingly, the chiral Cu(II) complex of the Schiff base derived from (R)‐2‐phenylglycinol and 2‐hydroxy‐1‐naphthaldehyde was found to catalyze the same reaction under solid‐liquid conditions with comparable enantioselectivity (up to 60% ee) with respect to known cinchona alkaloid catalysts. The solvent/base‐system parameter was shown to control the optimal catalytic activity. Chirality 27:944–950, 2015. © 2015 Wiley Periodicals, Inc.     

Graphene Layers‐Wrapped Fe/Fe5C2 Nanoparticles Supported on N‐doped Graphene Nanosheets for Highly Efficient Oxygen Reduction

Synthesis of highly efficient nonprecious metal electrocatalysts for the oxygen reduction reaction (ORR) superior to platinum (Pt) is still a big challenge. Herein, a new highly active ORR electrocatalyst is reported based on graphene layers‐wrapped Fe/Fe₅C₂ nanoparticles supported on N‐doped graphene nanosheets (GL‐Fe/Fe₅C₂/NG) through simply annealing a mixture of bulk graphitic carbon nitride (g‐C₃N₄) and ferrocene. An interesting exfoliation–denitrogen mechanism underlying the conversion of bulk g‐C₃N₄ into N‐doped graphene nanosheets is revealed. Owing to the high graphitic degree, optimum N‐doping level and sufficient active sites from the graphene layers‐wrapped Fe/Fe₅C₂ nanoparticles, the as‐prepared GL‐Fe/Fe₅C₂/NG electrocatalyst obtained at 800 °C exhibits outstanding ORR activity with a 20 mV more positive half‐wave potential than the commercial Pt/C catalyst in 0.1 m KOH solution and a comparable onset potential of 0.98 V. This makes GL‐Fe/Fe₅C₂/NG an outstanding electrocatalyst for ORR in alkaline solution.     

Design of Carbon Nanotube‐Based Gas‐Diffusion Cathode for O2 Reduction by Multicopper Oxidases

Multicopper oxidases, such as laccase or bilirubin oxidase, are known to reduce molecular oxygen at very high redox potentials, which makes them attractive biocatalysts for enzymatic cathodes in biological fuel cells. By designing an enzymatic gas‐diffusion electrode, molecular oxygen can be supplied through the gaseous phase, avoiding solubility and diffusion limitations typically associated with liquid electrolytes. In doing so, the current density of enzymatic cathodes can theoretically be enhanced. This publication presents a material study of carbon/Teflon composites that aim to optimize the functionality of the gas‐diffusion and catalytic layers for application in enzymatic systems. The modification of the catalytic layer with multiwalled carbon nanotubes, for example, creates the basis for stronger π–π stacking interactions through tethered enzymatic linkers, such as pyrenes or perylene derivates. Cyclic voltammograms show the effective direct electron contact of laccase with carbon nanotube‐modified electrodes via tethered crosslinking molecules as a model system. The polarization behavior of laccase‐modified gas‐diffusion electrodes reveals open‐circuit potentials of +550 mV (versus Ag/AgCl) and current densities approaching 0.5 mA cm² (at zero potential) in air‐breathing mode.