High resolution fossil fuel combustion CO 2 emission fluxes for the United States Kevin R. Gurney 1 , Daniel L. Mendoza 1 , Yuyu Zhou 1 , Marc L. Fischer 2 , Chris C. Miller 1 , Sarath Geethakumar 1 , Stephane de la Rue du Can 2 Department of Earth and Atmospheric Sciences/Department of Agronomy, Purdue University, 550 Stadium Mall Drive, West Lafayette, IN 47907; 2 Atmospheric Science Department, Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, 90K-125, Berkeley, CA 94720 Corresponding Author: Kevin Robert Gurney Department of Earth and Atmospheric Sciences/Department of Agronomy, Purdue University, 550 Stadium Mall Drive, West Lafayette, IN 47907

High resolution fossil fuel combustion CO2 emission fluxes for theUnited States

Current energy and environmental challenges demand the development and design of multifunctional porous materials with tunable properties for catalysis, water purification, and energy conversion and storage. Because of their amenability to de novo reticular chemistry, metal–organic frameworks (MOFs) have become key materials in this area. However, their usefulness is often limited by low chemical stability, conductivity and inappropriate pore sizes. Conductive two-dimensional (2D) materials with robust structural skeletons and/or functionalized surfaces can form stabilizing interactions with MOF components, enabling the fabrication of MOF nanocomposites with tunable pore characteristics. Graphene and its functional derivatives are the largest class of 2D materials and possess remarkable compositional versatility, structural diversity, and controllable surface chemistry. Here, we critically review current knowledge concerning the growth, structure, and properties of graphene derivatives, MOFs, and their graphene@MOF composites as well as the associated structure–property–performance relationships. Synthetic strategies for preparing graphene@MOF composites and tuning their properties are also comprehensively reviewed together with their applications in gas storage/separation, water purification, catalysis (organo-, electro-, and photocatalysis), and electrochemical energy storage and conversion. Current challenges in the development of graphene@MOF hybrids and their practical applications are addressed, revealing areas for future investigation. We hope that this review will inspire further exploration of new graphene@MOF hybrids for energy, electronic, biomedical, and photocatalysis applications as well as studies on previously unreported properties of known hybrids to reveal potential “diamonds in the rough”.

https://pubs.acs.org/doi/pdf/10.1021/acs.chemrev.2c00270

Graphene-Based Metal–Organic Framework Hybrids for Applications in Catalysis, Environmental, and Energy Technologies

Li–O2 batteries are believed to be practical energy storage devices for electric vehicles due to their ultrahigh theoretical specific energy. The major challenges are the poor interface stability of the electrode/electrolyte caused by the degradation of the electrolyte and cathode and the formation of lithium dendrites, which drain the battery life. Meanwhile, high temperatures will accelerate the interface reaction and lead to the rapid death of batteries. Herein, we present a multifunctional quasi-solid-state electrolyte based on a metal–organic framework (MOF) and an ionic liquid (IL) to simultaneously stabilize the cathode and protect the Li anode in Li–O2 batteries at high temperatures. The electrolyte has negligible volatility and good wettability with the electrodes, and the synergistic effect of the IL and MOF suppresses the lithium dendrite growth by forming a homogeneous Li+ flux. The Li–O2 battery with this electrolyte exhibited a high discharge capacity and improved cycle life (>1100 h) with a low overpotential at 60 °C. Besides, the Li–O2 battery delivered improved electrochemical performances at a higher temperature of 80 °C due to the superior thermal stability of the electrolyte. These results indicate that the quasi-solid-state electrolyte can be a potential strategy for the commercialization of Li–O2 batteries. 

Enhancing the Long Cycle Performance of Li–O2 Batteries at High Temperatures Using Metal–Organic Framework-Based Electrolytes

Mixed matrix membranes (MMMs) have attracted significant attention in the field of CO2 separation because MMMs have potential to overcome an undesirable "trade-off" effect. In this study, the beaded nanofillers of ZIF-8@aminoclay (ZIF-8@AC) were synthesized using an in situ growth method, and they were doped into a Pebax MH 1657 (Pebax) matrix to fabricate MMMs for efficient CO2 separation. The beaded structure was formed by ZIF-8 particles joined together during the process of AC coating on the ZIF-8 surface. ZIF-8@AC played a vital role in the improvement of gas separation performance. It was mainly attributed to the following reasons: First, the inherent micropores of ZIF-8 constructed the internal pathways for gas transport in the beaded nanofillers, benefiting the improvement of gas permeability. Second, the staggered AC layers constructed the external pathways for gas transport in the beaded nanofillers, increasing the tortuosity of gas transport for larger molecules and favoring the improvement of gas selectivity. Therefore, the internal and external pathways of ZIF-8@AC co-constructed the dual-transport pathways for CO2 transport in MMMs. In addition, the abundant amino groups of the beaded nanofillers provided abounding carriers for CO2, facilitating CO2 transport in the dual-transport pathways. Therefore, the CO2 separation performance of Pebax/ZIF-8@AC-1 MMMs was significantly improved. The CO2 permeability and CO2/CH4 separation factor of Pebax/ZIF-8@AC-1-7 MMM were 620 ± 10 Barrer and 40 ± 0.4, which were 2.3 and 1.6 times those of a pure Pebax membrane, respectively. Furthermore, the CO2/CH4 separation performance of Pebax/ZIF-8@AC-1-7 MMM overcame successfully the "trade-off" effect and approached the 2019 upper bound. It is a novel strategy to design a beaded nanofiller doped into MMMs for carbon capture.

Constructing Dual-Transport Pathways by Incorporating Beaded Nanofillers in Mixed Matrix Membranes for Efficient CO2 Separation.

Engineering CO2-philic pathway via grafting poly(ethylene glycol) on graphene oxide for mixed matrix membranes with high CO2 permeance

High-performance, thin-film mixed-matrix membranes (MMMs) on a porous support have been developed, using zeolitic imidazole framework (ZIF) decorated graphene oxide (GO) as a filler, dispersed in a...

Ultrathin, Highly Permeable Graphene Oxide/Zeolitic Imidazole Framework Polymeric Mixed-Matrix Composite Membranes: Engineering the CO2-Philic Pathway

Preparation of Co9S8 nanostructure with double comb copolymer derived mesoporous carbon for solar energy conversion catalyst

High-voltage solar energy conversion based on ZIF-67-derived binary redox-quasi-solid-state electrolyte

We present highly mechanical strength and ionic conductive solid-state electrolyte membranes based on amphiphilic double comb copolymer, i.e., poly(vinylidene chloride)-graft-poly(methyl methacrylate) (PVDC-g-PMMA) synthesized through atomic transfer radical polymerization (ATRP). Well-defined nanophase-separated amphiphilic double comb copolymers are complexed with two types of Li salts (LiTFSI and LiClO4) to form a solid-state electrolyte membrane. Compared to other types, the highest ionic conductivity of the solid-state electrolyte membranes is observed in an amphiphilic double comb copolymer with PVDC-g-PMMA/LiTFSI, due to the synergy of the dissociability of TFSI− and the hopping transport of lithium ions facilitated by PMMA chains. Moreover, the lowest activation energy (0.15 eV) and excellent ionic conductivity (1.3 × 10−3 S cm−1) are also observed in the same solid-state electrolyte membranes at room temperature.

Eunho Song

Papers

Ultrathin, Highly Permeable Graphene Oxide/Zeolitic Imidazole Framework Polymeric Mixed-Matrix Composite Membranes: Engineering the CO2-Philic Pathway

Preparation of Co9S8 nanostructure with double comb copolymer derived mesoporous carbon for solar energy conversion catalyst

High-voltage solar energy conversion based on ZIF-67-derived binary redox-quasi-solid-state electrolyte

Designing double comb copolymer as highly lithium ionic conductive solid-state electrolyte membranes