Graphdiyne/Graphene Heterostructure: A Universal 2D Scaffold Anchoring Monodispersed Transition-Metal Phthalocyanines for Selective and Durable CO₂ Electroreduction

Abstract

Electrochemical CO 2 reduction (CO 2 R) is a sustainable way of producing carbon-neutral fuels, yet the efficiency is limited by its sluggish kinetics and complex reaction pathways. Developing active, selective, and stable CO 2 R electrocatalysts is challenging and entails intelligent material structure design and tailoring. Here we show a graphdiyne/graphene (GDY/ G) heterostructure as a 2D conductive scaffold to anchor monodispersed cobalt phthalocyanine (CoPc) and reduce CO 2 with an appreciable activity, selectivity, and durability. Advanced characterizations, e.g., synchrotron-based X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculation disclose that the strong electronic coupling between GDY and CoPc, together with the high surface area, abundant reactive centers, and electron conductivity provided by graphene, synergistically contribute to this distinguished electrocatalytic performance. Electrochemical measurements revealed a high FE CO of 96% at a partial current density of 12 mA cm −2 in a H-cell and an FE CO of 97% at 100 mA cm −2 in a liquid flow cell, along with a durability over 24 h. The per-site turnover frequency of CoPc reaches 37 s −1 at −1.0 V vs RHE, outperforming most of the reported phthalocyanine-and porphyrin-based electrocatalysts. The usage of the GDY/G heterostructure as a scaffold can be further extended to other organometallic complexes beyond CoPc. Our findings lend credence to the prospect of the GDY/G hybrid contributing to the design of single-molecule dispersed CO 2 R catalysts for sustainable energy conversion.

Entanglement of Spatial and Energy Segmentation for C1 Pathways in CO2 Reduction on Carbon Skeleton Supported Atomic Catalysts

“…[42][43][44][45] In comparison, the experimental progress of GDY-based electrocatalyst is still limited. Zhang et al have reported the synthesis of graphdiyne/graphene heterostructure to anchor monodispersed cobalt phthalocyanine (CoPc) with a high FE of 96% for CO. [46] Later, Wang and Yuan's groups have reported the stabilization of Cu/Ni alloy and Ag nanoparticles on GDY for high FE of CO generation. [47,48] Although current experiments are still at a relatively early stage, intensive theoretical investigations have fully proven the potential of GDY-based electrocatalysts for CO 2 RR.…”

Promoting ethylene production over a wide potential window on Cu crystallites induced and stabilized via current shock and charge delocalization

“…Previous studies showed that the substrates for catalyst loading, in most cases the carbon support, play a critical role in steering the CO 2 RR pathway and stabilizing the catalytic process 19 , 20 . For instance, Strasser and colleagues 21 showed that the dispersion of Cu 2 O nanocubes on a carbon support sharply shifted the selectivity pattern toward C 1 , whereas its unsupported counterpart achieved a sustained C 2+ Faradaic efficiency (FE).…”

Self‐Co‐Electrolysis for Co‐Production of Phosphate and Hydrogen in Neutral Phosphate Buffer Electrolyte

“…[ 17 ] In addition, the pre‐edge peaks located at 7706 eV can be assigned to the 1s for 3d transition, indicating a centrosymmetric coordination structure of the Co atoms in the CoP‐based catalysts. [ 18 ] The coordination structure was also investigated using Fourier transform extended XAFS (FT‐EXAFS) spectroscopy (Figure 2f). The main peak at 1.7 Å corresponds to the Co‐P coordination shells, and the effects of N and Cu on this peak correspond to the effects of these elements in the XPS and XANES results.…”