Interfacial Water Tuning by Intermolecular Spacing for Stable CO2 Electroreduction to C2+ Products

Electroreduction of CO₂ to multi-carbon (C₂₊) products is a promising approach for utilization of renewable energy, in which the interfacial water quantity is critical for both the C₂₊ product selectivity and the stability of Cu-based electrocatalytic sites. Functionalization of long-chain alkyl molecules on a catalyst surface can help to increase its stability, while it also tends to block the transport of water, thus inhibiting the C₂₊ product formation. Herein, we demonstrate the fine tuning of interfacial water by surface assembly of toluene on Cu nanosheets, allowing for sustained and enriched CO₂ supply but retarded water transfer to catalytic surface. Compared to bare Cu with fast cathodic corrosion and long-chain alkyl-modified Cu with main CO product, the toluene assembly on Cu nanosheet surface enabled a high Faradaic efficiency of 78 % for C₂₊ and a partial current density of 1.81 A cm⁻². The toluene-modified Cu catalyst further exhibited highly stable CO₂-to-C₂H₄ conversion of 400 h in a membrane-electrode-assembly electrolyzer, suggesting the attractive feature for both efficient C₂₊ selectivity and excellent stability.     

A new black to highly transmissive switching bilayer polymer composite films with electroactive pEA as a color buffer layer for improving electrochromic stability

Two reported D-A-D monomers based on 3,4-ethylenedioxythiophene (EDOT) were selected for electrochemical copolymerization to obtain copolymer film, named pRG. Then, a soluble polymer poly[3,4-ethylenedioxythiophene-alt-3,4-bis([2-ethylhexyl]oxy)thiophene] (pEA) based on the EDOT derivative was screened out, which is complementary to the absorption trough of the pRG film in visible region and matched with its working potential. The bilayer composite film pRG/pEA was obtained by spinning pEA basement membrane on fluorine doped tin oxide (FTO) coated glass surface, and then in situ electrochemical polymerization of pRG film. Compared to the pRG monolayer film, the bilayer composite film shows a more saturated black color in the neutral state and significant improvement on cyclic stability (only decreased by 1.7% after 250 cycles, while pRG film decreased by 17.1%). The introduction of pEA buffer layer not only achieves the full spectral absorption of the composite film in the visible region, but also significantly improves the cyclic stability of the bilayer composite film. The assembled EC prototype device based on the pRG/pEA composite film exhibits a “black to high transmission” reversible switch. Finally, this method combining electrochemical copolymerization, spin-coating, lamination and other methods provides a new research idea for designing and preparing black to transmissive electrochromic materials.     

Synergistic Combination of Reductive Covalent Functionalization and Atomic Layer Deposition—Towards Spatially Defined Graphene-Organic-Inorganic Heterostructures

Three-dimensionally (3D) well-ordered and highly integrated graphene hybrid architectures are considered to be next-generation multifunctional graphene materials but still remain elusive. Here, we report the first realization of unprecedented 3D-patterned graphene nano-ensembles composed of a graphene monolayer, a tailor-made structured organophenyl layer, and three metal oxide films, providing the first example of such a hybrid nano-architecture. These spatially resolved and hierarchically structured quinary hybrids are generated via a two-dimensional (2D)-functionalization-mediated atomic layer deposition growth process, involving an initial lateral molecular programming of the graphene lattice via lithography-assisted 2D functionalization and a subsequent stepwise molecular assembly in these regions in the z-direction. Our breakthrough lays the foundation for the construction of emerging 3D-patterned graphene heterostructures.