Covalent Organic Framework Ionomer Steering the CO2 Electroreduction Pathway on Cu at Industrial-Grade Current Density.

CO2 electroreduction holds great promise for addressing global energy and sustainability challenges. Copper (Cu) shows great potential for effective conversion of CO2 toward specific value-added and/or high-energy-density products. However, its limitation lies in relatively low product selectivity. Herein, we present that the CO2 reduction reaction (CO2RR) pathway on commercially available Cu can be rationally steered by modulating the microenvironment in the vicinity of the Cu surface with two-dimensional sulfonated covalent organic framework nanosheet (COF-NS)-based ionomers. Specifically, the selectivity toward methane (CH4) can be enhanced to more than 60% with the total current density up to 500 mA cm-2 in flow cells in both acidic (pH = 2) and alkaline (pH = 14) electrolytes. The COF-NS, characterized by abundant apertures, can promote the accumulation of CO2 and K+ near the catalyst surface, alter the adsorption energy and surface coverage of *CO, facilitate the dissociation of H2O, and finally modulate the reaction pathway for the CO2RR. Our approach demonstrates the rational modulation of reaction interfaces for the CO2RR utilizing porous open framework ionomers, showcasing their potential practical applications.

Boosting CO2 Electroreduction on Bismuth Nanoplates with a Three-Dimensional Nitrogen-Doped Graphene Aerogel Matrix.

Electrochemical CO2 reduction reaction (CO2RR), which uses renewable electricity to produce high-value-added chemicals, offers an alternative clean path to the carbon cycle. However, bismuth-based catalysts show great potential for the conversion of CO2 and water to formate, but their overall efficiency is still hampered by the weak CO2 adsorption, low electrical conductivity, and slow mass transfer of CO2 molecules. Herein, we report that a rationally modulated nitrogen-doped graphene aerogel matrix (NGA) can significantly enhance the CO2RR performance of bismuth nanoplates (BiNPs) by both modulating the electronic structure of bismuth and regulating the interface for chemical reaction and mass transfer environments. In particular, the NGA prepared by reducing graphene oxide (GO) with hydrazine hydrate (denoted as NGAhdrz) exhibits significantly enhanced strong metal-support interaction (SMSI), increased specific surface area, strengthened CO2 adsorption, and modulated wettability. As a result, the Bi/NGAhdrz exhibits significantly boosted CO2RR properties, with a Faradaic efficiency (FE) of 96.4% at a current density of 51.4 mA cm-2 for formate evolution at a potential of -1.0 V versus reversible hydrogen electrode (vs RHE) in aqueous solution under ambient conditions.

Ultrathin Dendritic Pd-Ag Nanoplates for Efficient and Durable Electrocatalytic Reduction of CO2 to Formate.

CO2 reduction reactions (CO2 RR) powered by renewable electricity can directly convert CO2 to hydrocarbons and fix the sustainable but intermittent energy (e. g., sunlight, wind, etc.) in stable and portable chemical fuels. Advanced catalysts boosting CO2 RR with high activity, selectivity, and durability at low overpotentials are of great importance but still elusive. Here, we report that the ultrathin Pd-Ag dendritic nanoplates (PdAg DNPs) exhibited boosted activity, selectivity, and stability for producing formate from CO2 at a very low overpotential in aqueous solutions under ambient conditions. As a result, the PdAg DNPs exhibited a Faradaic efficiency (FE) for formate of 91% and a cathodic energy efficiency (EE) of ∼90% at the potential of -0.2 V versus reversible hydrogen electrode (vs. RHE), showing significantly enhanced durability as compared with pure Pd catalysts. Our strategy represents a rational catalyst design by engineering the surface geometrical and electronic structures of metal nanocrystals and may find more applicability in future electrocatalysis.

A Triptycene-Based 2D MOF with Vertically Extended Structure for Improving the Electrocatalytic Performance of CO2 to Methane.

Two-dimensional conductive metal-organic frameworks (2D-c-MOFs) have attracted extensive attention owing to their unique structures and physical-chemical properties. However, the planarly extended structure of 2D-c-MOFs usually limited the accessibility of the active sites. Herein, we designed a triptycene-based 2D vertically conductive MOF (2D-vc-MOF) by coordinating 2,3,6,7,14,15-hexahydroxyltriptycene (HHTC) with Cu2+ . The vertically extended 2D-vc-MOF(Cu) possesses a weak interlayer interaction, which leads to a facile exfoliation to the nanosheet. Compared with the classical 2D-c-MOFs with planarly extended 2D structures, 2D-vc-MOF(Cu) exhibits a 100 % increased catalytic activity in terms of turnover number and a two-fold increased selectivity. Density functional theory (DFT) calculations further revealed that higher activity originated from the lower energy barriers of the vertically extended 2D structures during the CO2 reduction reaction process.

Controlled Synthesis of Intermetallic Au2 Bi Nanocrystals and Au2 Bi/Bi Hetero-Nanocrystals with Promoted Electrocatalytic CO2 Reduction Properties.

The electrocatalytic properties of metal nanoparticles (NPs) strongly depend on their compositions and structures. Rational design of alloys and/or heterostructures provides additional approaches to modifying their surface geometric and electronic structures for optimized electrocatalytic performance. Here, a solution synthesis of freestanding intermetallic Au2 Bi NPs, the heterostructures of Au2 Bi/Bi hetero-NPs, and their promoted electrocatalytic CO2 reduction reaction (CO2 RR) performances were reported. It was revealed that the formation and in-situ conversion of heterogeneous seeds (e. g., Au) were of vital importance for the formation of intermetallic Au2 Bi and Au2 Bi/Bi hetero-NPs. It was also found that the Au components would act as the structure promoter moderating the binding strength for key intermediates on Bi surfaces. The alloying of Bi with Au and the formation of heterogeneous Au2 Bi/Bi interfaces would create more surface active sites with modulated electronic structures and stronger adsorption strengths for key intermediates, promoting the CO2 -to-HCOOH conversion with high activity and selectivity. This work presents a novel route for preparing intermetallic nanomaterials with modulated surface geometric/electric structures and promoting their electrocatalytic activities with alloying effects and interfacial effects. Such strategy may find wide application in catalyst design and synthesis for more electrocatalytic reactions.

Promoting the Electrocatalytic Reduction of CO2 on Ultrathin Porous Bismuth Nanosheets with Tunable Surface-Active Sites and Local pH Environments.

Electrochemical CO2 reduction reaction (CO2RR) yielding value-added chemicals provides a sustainable approach for renewable energy storage and conversion. Bismuth-based catalysts prove to be promising candidates for converting CO2 and water into formate but still suffer from poor selectivity and activity and/or sluggish kinetics. Here, we report that ultrathin porous Bi nanosheets (Bi-PNS) can be prepared through a controlled solvothermal protocol. Compared with smooth Bi nanoparticles (Bi-NPs), the ultrathin, rough, and porous Bi-PNS provide more active sites with higher intrinsic reactivities for CO2RR. Moreover, such high activity further increases the local pH in the vicinity of the catalyst surfaces during electrolysis and thus suppresses the competing hydrogen evolution reaction. As a result, the Bi-PNS exhibit significantly boosted CO2RR properties, showing a Faradaic efficiency of 95% with an effective current density of 45 mA cm-2 for formate evolution at the potential of -1.0 V versus reversible hydrogen electrode.

Modulating the electrocatalytic CO2 reduction performances of bismuth nanoparticles with carbon substrates with controlled degrees of oxidation.

The catalytic performances of metal nanoparticles can be widely tuned and promoted by the metal-support interactions. Here, we report that the morphologies and electrocatalytic CO2 reduction reaction (CO2RR) properties of bismuth nanoparticles (BiNPs) can be rationally modulated by their interactions with carbon black (CB) supports by controlling the degree of surface oxidation. Appropriately oxidized CB supports can provide sufficient oxygen-containing groups for anchoring BiNPs with tunable sizes and surface areas, desirable key intermediate adsorption abilities, appropriate surface wettability, and adequate electron transfer abilities. As a result, the optimized Bi/CB catalysts exhibited a promoted CO2RR performance with a Faradaic efficiency of 94% and a current density of 16.7 mA cm-2 for HCOO- at -0.9 V versus a reversible hydrogen electrode. Our results demonstrate the significance of regulating the interactions between supports and metal nanoparticles for both synthesis of the catalyst and electrolysis applications, which may find broader applicability in more electrocatalyst designs.

The Synthesis of Hexaazatrinaphthylene-Based 2D Conjugated Copper Metal-Organic Framework for Highly Selective and Stable Electroreduction of CO2 to Methane.

2D conjugated MOFs have attracted significant interests in recent years owing to their special structural features and promising physical and chemical properties. These intriguing attributes, to a large extent, stem from the nature of incorporated ligands. The available ligands for the construction of 2D conjugated MOFs are still limited, especially those that have heteroatoms included and exposed to the pores. In this work, we designed and synthesized a highly symmetric hexaazatrinaphthylene (HATNA)-based ligand with two different coordination sites. Through selective coordination, a highly crystalline and porous 2D conjugated copper metal-organic framework was constructed. Due to the synergic effects of HATNA and copper catecholate node, this HATNA-based 2D conjugated MOF can mediate the electrocatalytic reduction of CO2 to methane with high selectivity of 78 % at high current density of 8.2 milliamperes per square centimetre (mA cm-2 ) for long durability over 12 hours.

Morphology-dependent electrocatalytic nitrogen reduction on Ag triangular nanoplates.

Electrocatalytic nitrogen reduction reactions (ENRR) can produce ammonia from nitrogen and water under ambient conditions. Here, we report the morphology-dependent electro-catalytic nitrogen reduction on Ag triangular nanoplates. Boosted by potassium cations, Ag triangular nanoplates with sharp edges exhibit a high faradaic efficiency of 25% with an ammonia yield of 58.5 mg gAg-1 h-1 at a low overpotential of -0.25 V vs. RHE. In comparison, rounded Ag nanoparticles mainly enclosed by {111} and {100} surfaces show a much smaller faradaic efficiency of 16% and ammonia yield of 38 mg gAg-1 h-1 at a larger overpotential (-0.35 V vs. RHE).