Metal–organic frameworks (MOFs) are promising materials for electrocatalysis; however, lack of electrical conductivity in the majority of existing MOFs limits their effective utilization in the field. Herein, an excellent catalytic activity of a 2D copper (Cu)‐based conductive MOF, copper tetrahydroxyquinone (CuTHQ), is reported for aqueous CO2reduction reaction (CO2RR) at low overpotentials. It is revealed that CuTHQ nanoflakes (NFs) with an average lateral size of 140 nm exhibit a negligible overpotential of 16 mV for the activation of this reaction, a high current density of ≈173 mA cm−2at −0.45 V versus RHE, an average Faradaic efficiency (F.E.) of ≈91% toward CO production, and a remarkable turnover frequency as high as ≈20.82 s−1. In the low overpotential range, the obtained CO formation current density is more than 35 and 25 times higher compared to state‐of‐the‐art MOF and MOF‐derived catalysts, respectively. The operando Cu K‐edge X‐ray absorption near edge spectroscopy and density functional theory calculations reveal the existence of reduced Cu (Cu+) during CO2RR which reversibly returns to Cu2+after the reaction. The outstanding CO2catalytic functionality of conductive MOFs (c‐MOFs) can open a way toward high‐energy‐density electrochemical systems.
- Award ID(s):
- 1849206
- NSF-PAR ID:
- 10251428
- Date Published:
- Journal Name:
- RSC Advances
- Volume:
- 11
- Issue:
- 8
- ISSN:
- 2046-2069
- Page Range / eLocation ID:
- 4472 to 4477
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Abstract A simple and environmentally‐friendly approach was developed to synthesize 2D CuO nanosheets using electrochemical deposition. The formed 2D CuO nanosheets (NSs) exhibit numerous advantageous properties such as no toxicity, high electrical conductivity, large active surface area, and a p‐type semiconducting nature with a band gap of 1.2 eV. A sensitive electrochemical sensor was constructed for the amperometric detection of glucose to take advantage of these characteristics. The fabricated sensor displayed an excellent sensitivity of 2710 μA mM−1 cm−2along with a wide linear range of 0.001–1.0 mM and a lower limit of detection of 0.8 μM (S/N=3). Additionally, the modified electrode possesses high selectivity and good stability. The outstanding electrocatalytic performance of the electrode is attributed to a large active surface area, unique structural morphology, and the high conductivity of the 2D CuO nanosheets.
-
more » « less
MXenes, a new class of 2D transition metal carbides and carbonitrides, show great promise in supercapacitors, Li‐ion batteries, fuel cells, and sensor applications. A unique combination of their metallic conductivity, hydrophilic surface, and excellent mechanical properties renders them attractive for transparent conductive electrode application. Here, a simple, scalable method is proposed to fabricate transparent conductive thin films using delaminated Ti3C2MXene flakes by spray coating. Homogenous films, 5–70 nm thick, are produced at ambient conditions over a large area as shown by scanning electron microscopy and atomic force microscopy. The sheet resistances (
Rs ) range from 0.5 to 8 kΩ sq−1at 40% to 90% transmittance, respectively, which corresponds to figures of merit (the ratio of electronic to optical conductivities,σ DC/σ opt) around 0.5–0.7. Flexible, transparent, and conductive films are also produced and exhibit stableRs values at up to 5 mm bend radii. Furthermore, the films' optoelectronic properties are tuned by chemical or electrochemical intercalation of cations. The films show reversible changes of transmittance in the UV–visible region during electrochemical intercalation/deintercalation of tetramethylammonium hydroxide. This work shows the potential of MXenes to be used as transparent conductors in electronic, electrochromic, and sensor applications. -
High-voltage lithium metal batteries (LMBs) are a promising high-energy density energy storage system. However, their practical implementations are impeded by short lifespan due to uncontrolled lithium dendrite growth, narrow electrochemical stability window, and safety concerns of liquid electrolytes. Here, a porous composite aerogel is reported as the gel electrolyte (GE) matrix, made of metal–organic framework (MOF)@bacterial cellulose (BC), to enable long-life LMBs under high voltage. The effectiveness of suppressing dendrite growth is achieved by regulating ion deposition and facilitating ion conduction. Specifically, two hierarchical mesoporous Zr-based MOFs with different organic linkers, that is, UiO-66 and NH2-UiO-66, are embedded into BC aerogel skeletons. The results indicate that NH2-UiO-66 with anionphilic linkers is more effective in increasing the Li+ transference number; the intermolecular interactions between BC and NH2-UiO-66 markedly increase the electrochemical stability. The resulting GE shows high ionic conductivity (≈1 mS cm−1), high Li+ transference number (0.82), wide electrochemical stability window (4.9 V), and excellent thermal stability. Incorporating this GE in a symmetrical Li cell successfully prolongs the cycle life to 1200 h. Paired with the Ni-rich LiNiCoAlO2 (Ni: Co: Al = 8.15:1.5:0.35, NCA) cathode, the NH2-UiO-66@BC GE significantly improves the capacity, rate performance, and cycle stability, manifesting its feasibility to operate under high voltage.more » « less
-
more » « less
Abstract Intercalation in few‐layer (2D) materials is a rapidly growing area of research to develop next‐generation energy‐storage and optoelectronic devices, including batteries, sensors, transistors, and electrically tunable displays. Identifying fundamental differences between intercalation in bulk and 2D materials will play a key role in developing functional devices. Herein, advances in few‐layer intercalation are addressed in the historical context of bulk intercalation. First, synthesis methods and structural properties are discussed, emphasizing electrochemical techniques, the mechanism of intercalation, and the formation of a solid‐electrolyte interphase. To address fundamental differences between bulk and 2D materials, scaling relationships describe how intercalation kinetics, structure, and electronic and optical properties depend on material thickness and lateral dimension. Here, diffusion rates, pseudocapacity, limits of staging, and electronic structure are compared for bulk and 2D materials. Next, the optoelectronic properties are summarized, focusing on charge transfer, conductivity, and electronic structure. For energy devices, opportunities also emerge to design van der Waals heterostructures with high capacities and excellent cycling performance. Initial studies of heterostructured electrodes are compared to state‐of‐the‐art battery materials. Finally, challenges and opportunities are presented for 2D materials in energy and optoelectronic applications, along with promising research directions in synthesis and characterization to engineer 2D materials for superior devices.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0ra10522h
