2024 New's Items

Iron homo- and heterobimetallic complexes supported by a symmetrical dinucleating ligand

Pablo R
See MS
Gonzalez O
Ford RC
Nicolay A
Rao G
Britt RD
Bediako DK
Tilley TD
2024

The selective synthesis of biomimetic Fe/Mn complexes able to mimic the geometry and catalytic activity of enzymes possessing this cofactor is still a challenge. Herein, we discuss the stepwise synthesis, characterization, and magnetic properties of a Fe(II)/Mn(II) species and related Fe(II)/Fe(II) complexes.

The role of manganese in CoMnOx catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis

Chen H
Lian Z
Zhao X
Wan J
Pieters PF
Oliver-Meseguer J
Yang J
Pach E
Carenco S
Treps L
Liakakos N
Shan Y
Altoe V
Wong E
Zhuo Z
Yang F
Su J
Guo J
Blum M
Lapidus SH
Hunt A
Waluyo I
Ogasawara H
Zheng H
Yang P
Bell AT
López N
Salmeron M
2024

Cobalt is an efficient catalyst for Fischer−Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H2) with enhanced selectivity for long-chain hydrocarbons when promoted by Manganese. However, the molecular scale origin of the enhancement remains unclear. Here we present an experimental and theoretical study using model catalysts consisting of crystalline CoMnOx nanoparticles and thin films, where Co and Mn are mixed at the sub-nm scale. Employing TEM and in-situ X-ray spectroscopies (XRD, APXPS, and XAS), we determine the catalyst’s atomic structure, chemical...

Particle on a Rod: Surface-Tethered Catalyst on CdS Nanorods for Enzymatically Active Nicotinamide Cofactor Generation

Jayasinghe L
Wei J
Kim J
Lineberry E
Yang P
2024

The photochemical generation of nicotinamide cofactor 1,4- NADH, facilitated by inorganic photosensitizers, emerges as a promising model system for investigating charge transfer phenomena at the interface of semiconductors and bacteria, with implications for enhancing photosynthetic biohybrid systems (PBSs). However, extant semiconductor nanocrystal model systems suffer from achieving optimal conversion efficiency under visible light. This study investigates quasi-one-dimensional CdS nanorods as superior light absorbers, surface modified with catalyst Cp*Rh(4,4′-COOH-bpy)Cl2 to produce...

Dynamic Evolution of Copper Nanowires during CO2 Reduction Probed by Operando Electrochemical 4D-STEM and X‑ray Spectroscopy

Yang Y
Shi C
Feijóo J
Jin J
Chen C
Han Y
Yang P
2024

Nanowires have emerged as an important family of one-dimensional (1D) nanomaterials owing to their exceptional optical, electrical, and chemical properties. In particular, Cu nanowires (NWs) show promising applications in catalyzing the challenging electrochemical CO2 reduction reaction (CO2RR) to valuable chemical fuels. Despite early reports showing morphological changes of Cu NWs after CO2RR processes, their structural evolution and the resulting exact nature of active Cu sites remain largely elusive, which calls for the development of multimodal operando time-resolved nm-scale methods...

A red-light-powered silicon nanowire biophotochemical diode for simultaneous CO2 reduction and glycerol valorization

Kim J
Lin JA
Kim J
Roh I
Lee S
Yang P
2024

A bias-free photochemical diode, in which a p-type photocathode is connected to an n-type photoanode to harness light for driving photoelectrochemical reduction and oxidation pairs, serves as a platform for realizing light-driven fuel generation from CO2. However, the conventional design, in which cathodic CO2 reduction is coupled with the anodic oxygen evolution reaction (OER), requires substantial energy input. Here we present a photochemical diode device that harnesses red light (740 nm) to simultaneously drive biophotocathodic CO2-to-multicarbon conversion and photoanodic glycerol...

Room-Temperature Ferroelectric Epitaxial Nanowire Arrays with Photoluminescence

Le HKD
Zhang Y
Behera P
Vailionis A
Phang A
Brinn R
Yang P
2024

The development of large-scale, high-quality ferroelectric semiconductor nanowire arrays with interesting light-emitting properties can address limitations in traditional wide-bandgap ferroelectrics, thus serving as building blocks for innovative device architectures and next-generation high-density optoelectronics. Here, we investigate the optical properties of ferroelectric CsGeX3 (X = Br, I) halide perovskite nanowires that are epitaxially grown on muscovite mica substrates by vapor phase deposition. Detailed structural characterizations reveal an incommensurate heteroepitaxial...

Complete miscibility of immiscible elements at the nanometre scale

Chen PC
Gao M
McCandler CA
Song C
Jin J
Yang Y
Maulana AL
Persson KA
Yang P
2024

Understanding the mixing behaviour of elements in a multielement material is important to control its structure and property. When the size of a multielement material is decreased to the nanoscale, the miscibility of elements in the nanomaterial often changes from its bulk counterpart. However, there is a lack of comprehensive and quantitative experimental insight into this process. Here we explored how the miscibility of Au and Rh evolves in nanoparticles of sizes varying from 4 to 1 nm and composition changing from 15% Au to 85% Au. We found that the two immiscible elements exhibit a...

Nanometre-resolved observation of electrochemical microenvironment formation at the nanoparticle–ligand interface

Shan Y
Zhao X
Guzman MF
Jana A
Chen S
Yu S
Ng KC
Roh I
Chen H
Altoe V
Corder SG
Bechtel HA
Qian J
Salmeron MB
Yang P
2024

The dynamic response of surface ligands on nanoparticles (NPs) to external stimuli critically determines the functionality of NP–ligand systems. For example, in electrocatalysis the collective dissociation of ligands on NP surfaces can lead to the creation of an NP/ordered-ligand interlayer, a microenvironment that is highly active and selective for CO2-to-CO conversion. However, the lack of in situ characterization techniques with high spatial resolution hampers a comprehensive molecular-level understanding of the mechanism of interlayer formation. Here we...

Crystalline Polyphenylene Covalent Organic Frameworks

Han X
Zhou Z
Wang K
Zheng Z
Neumann SE
Zhang H
Ma T
Yaghi OM
2023

The synthesis of crystalline polyphenylene covalent organic frameworks (COFs) was accomplished by linking fluorinated tris(4-acetylphenyl)benzene building units using aldol cyclotrimerization. The structures of the two COFs, reported here, were confirmed by powder X-ray diffraction techniques, Fourier transform infrared, and solid-state 13C CP/MAS NMR spectroscopy. The results showed that the COFs were porous and chemically stable in corrosive, harsh environments for at least 1 week. Accordingly, postsynthetically modified derivatives of these COFs using primary amines showed...

Harvesting Water from Air with High-Capacity, Stable Furan-Based Metal–Organic Frameworks

Alawadhi AH
Chheda S
Stroscio GD
Rong Z
Kurandina D
Nguyen HL
Rampal N
Zheng Z
Gagliardi L
Yaghi OM
2024

We synthesized two isoreticular furan-based metal–organic frameworks (MOFs), MOF-LA2-1(furan) and MOF-LA2-2(furan) with rod-like secondary building units (SBUs) featuring 1D channels, as sorbents for atmospheric water harvesting (LA = long arm). These aluminum-based MOFs demonstrated a combination of high water uptake and stability, exhibiting working capacities of 0.41 and 0.48 gwater/gMOF (under isobaric conditions of 1.70 kPa), respectively. Remarkably, both MOFs showed a negligible loss in water uptake after 165 adsorption–desorption cycles. These working...