2022 New's Items

Toward abiotic sugar synthesis from CO2 electrolysis

Cestellos-Blanco S
Louisia S
Ross MB
Li Y
Soland NE
Detomasi TC
Nomura DK
Cestellos Spradlin JN
Yang P
2022

Although steady progress has been achieved toward upcycling waste CO2 through diverse catalytic strategies, each approach has distinct limitations, hampering the generation of complex products like sugars. Here, we provide a roadmap that evaluates the feasibility associated with state-of-the-art electrochemical processes eligible for converting CO2...

An embedded interfacial network stabilizes inorganic CsPbI3 perovskite thin films

Steele JA ......
Yang P
Hofkens J
Speybroeck VV
Roeffaers MBJ
2022

The black perovskite phase of CsPbI3 is promising for optoelectronic applications; however, it is unstable under ambient conditions, transforming within minutes into an optically inactive yellow phase, a fact that has so far prevented its widespread adoption. Here we use coarse photolithography to embed a PbI2-based interfacial microstructure into otherwise-unstable CsPbI3 perovskite thin films and devices. Films fitted with a tessellating microgrid are rendered resistant to moisture-triggered decay and...

Exploration of the bio-analogous asymmetric C–C coupling mechanism in tandem CO2 electroreduction

Chen C
Yu S
Yang Y
Louisia S
Roh I
Jin J
Chen S
Chen P-C
Shan Y
Yang P
2022

C–C coupling is a critical step of CO2 fixation in constructing the carbon skeleton of value-added multicarbon products. The Wood–Ljungdahl pathway is an efficient natural process through which microbes transform CO2 into methyl and carbonyl groups and subsequently couple them together. This asymmetric coupling mechanism remains largely unexplored in inorganic CO2 electroreduction. Here we experimentally validate the asymmetric coupling pathway through isotope-labelled co-reduction experiments on a Cu...

Broadly Tunable Atmospheric Water Harvesting in Multivariate Metal–Organic Frameworks

Zheng Z
Hanikel N
Lyu H
Yaghi OM
2022

Development of multivariate metal–organic frameworks (MOFs) as derivatives of the state-of-art water-harvesting material MOF-303 {[Al(OH)(PZDC)], where PZDC2– is 1H-pyrazole-3,5-dicarboxylate} was shown to be a powerful tool to generate efficient water sorbents tailored to a given environmental condition. Herein, a new multivariate MOF-303-based water-harvesting framework series from readily available reactants is developed. The resulting MOFs exhibit a larger degree of tunability in the operational relative humidity range (16%), regeneration...

High-yield, green and scalable methods for producing MOF-303 for water harvesting from desert air

Zheng Z
Nguyen HL
Hanikel N
Li KK
Zhou Z
Ma T
Yaghi OM
2022

Metal–organic frameworks (MOFs) are excellent candidates for water harvesting from desert air. MOF-303 (Al(OH)(PZDC), where PZDC is 1-H-pyrazole-3,5-dicarboxylate), a robust and water-stable MOF, is a particularly promising water-harvesting sorbent that can take up water at low relative humidity and release it under mild heating. Accordingly, development of a facile, high-yield synthesis method for its production at scale is highly desirable. Here we report detailed protocols for the green, water-based preparation of MOF-303 on both gram and kilogram scales. Specifically...

System of sequences in multivariate reticular structures

Canossa S
Ji Z
Gropp C
Rong Z
Ploetz E
Wuttke S
Yaghi OM
2022

When variance is encountered in reticular structures such as metal–organic frameworks, it occurs as multiple kinds of functionalities bound and distributed in aperiodic lattices. In these multivariate systems, unknown spatial arrangements of functionalities create properties that go beyond those of their simple sum. It is therefore essential that we learn how to recognize, study and use these arrangements, and for this purpose we propose using the concept of sequences. Accordingly, we propose a classification system, outline a method for characterizing sequences and describe the...

Covalent Organic Frameworks for Carbon Dioxide Capture from Air

Lyu H
Li H
Hanikel N
Wang K
Yaghi OM
2022

We report the first covalent incorporation of reactive aliphatic amine species into covalent organic frameworks (COFs). This was achieved through the crystallization of an imine-linked COF, termed COF-609-Im, followed by conversion of its imine linkage to base-stable tetrahydroquinoline linkage through aza-Diels–Alder cycloaddition, and finally, the covalent incorporation of tris(3-aminopropyl)amine into the framework. The obtained COF-609 exhibits a 1360-fold increase in CO2 uptake capacity compared to the pristine framework and a further 29% enhancement in...

Hydrazine-Hydrazide-Linked Covalent Organic Frameworks for Water Harvesting

Nguyen HL
Gropp C
Hanikel N
Möckel A
Lund A
Yaghi OM
2022

We report a postsynthetic strategy and its implementation to make covalent organic frameworks (COFs) with irreversible hydrazide linkages. This involved the synthesis of three 2D and 3D hydrazine-linked frameworks and their partial oxidation. The linkage synthesis and functional group transformation─hydrazine and hydrazide─were evidenced by 15N multi-CP-MAS NMR. In addition, the isothermal water uptake profiles of these frameworks were studied, leading to the discovery of one hydrazine-hydrazide-linked COF suitable for water harvesting from air in arid...

Visualizing Pore Packing and Topology in MOFs

Lisensky GC
Yaghi OM
2022

Metal organic frameworks (MOFs) can have open pore structures with high surface areas and applications in hydrogen storage, carbon dioxide capture, water harvesting from air, chemical separations, and catalysis. The chemical structure of these crystalline solids can initially appear daunting. Simplification by considering the arrangement of the pores and by identifying the links and vertices as well as switching between multiple representations can make visualization of these structures accessible.

Large Cages of Zeolitic Imidazolate Frameworks

Wang H
Pei X
Kalmutzki MJ
Yang J
Yaghi OM
2022

The design and synthesis of permanently porous materials with extended cage structures is a long-standing challenge in chemistry. In this Account, we highlight the unique role of zeolitic imidazolate frameworks (ZIFs), a class of framework materials built from tetrahedral nodes connected through imidazolate linkers, in meeting this challenge and illustrate specific features that set ZIFs apart from other porous materials. The structures of ZIFs are characteristic of a variety of large, zeolite-like cages that are covalently connected with neighboring cages and fused in three-dimensional...