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The structural stability of nanocatalysts during electrochemical CO2 reduction (CO2RR) is crucial for practical applications. However, highly active nanocatalysts often reconstruct under reductive conditions, requiring stabilization strategies to maintain activity. Here, we demonstrate that the N-heterocyclic carbene (NHC) polymer stabilizes Au nanowire (NW) catalysts for selective CO2 reduction to CO over a broad potential range, enabling coupling with Cu NWs for one-step tandem conversion of CO2 to C2H4. By combining the hydrophobicity of the polystyrene chain and the strong binding of NHC to Au, the polymer stabilizes Au NWs and promotes CO2RR to CO with excellent selectivity (>90%) across −0.4 V to −1.0 V (vs RHE), a significantly broader range than unmodified Au NWs (−0.5 V to −0.7 V). Stable CO2RR at negative potentials yields a high jCO of 142 A/g Au at −1.0 V. In situ ATR-IR analysis indicates that the NHC polymer regulates the water microenvironment and suppresses hydrogen evolution at high overpotential. Moreover, NHC-Au NWs maintain excellent stability during 10 h of CO2RR testing, preserving the NW morphology and catalytic performance, while unmodified NWs degrade into nanoparticles with reduced activity and selectivity. NHC-Au NWs can be coupled with Cu NWs in a flow cell to catalyze CO2RR to C2H4 with 58% efficiency and a partial current density of 70 mA/cm2 (overall C2 product efficiency of 65%). This study presents an adaptable strategy to enhance the catalyst microenvironment, ensure stability, and enable efficient tandem CO2 conversion into value-added hydrocarbons. 

Abstract We present a new clustering-enabled regression approach to investigate how functional connectivity (FC) of the entire brain changes from childhood to old age. By applying this method to resting-state functional magnetic resonance imaging data aggregated from three Human Connectome Project studies, we cluster brain regions that undergo identical age-related changes in FC and reveal diverse patterns of these changes for different region clusters. While most brain connections between pairs of regions show minimal yet statistically significant FC changes with age, only a tiny proportion of connections exhibit practically significant age-related changes in FC. Among these connections, FC between region clusters from the same functional network tends to decrease over time, whereas FC between region clusters from different networks demonstrates various patterns of age-related changes. Moreover, our research uncovers sex-specific trends in FC changes. Females show much higher FC mainly within the default mode network, whereas males display higher FC across several more brain networks. These findings underscore the complexity and heterogeneity of FC changes in the brain throughout the lifespan. 

We summarize recent advances in the design of hybrid nanostructures through the combination of synthetic polymers and plasmonic nanoparticles (NPs). We categorize the synthetic methods of those polymer-coated metal NPs into two main strategies: direct encapsulation and chemical grafting, based on how NPs interact with polymers. In direct encapsulation, NPs with hydrophobic ligands are physically encapsulated into polymer micelles, primarily through hydrophobic interactions. We discuss strategies for controlling the loading numbers and locations of NPs within polymer micelles. On the other hand, polymer-grafted NPs (PGNPs) have synthetic polymers as ligands chemically grafted on NPs. We highlight that polymer ligands can asymmetrically coat metal NPs through hydrophobicity-driven phase segregation using homopolymers, BCPs and blocky random copolymers. This review provides insights into the methodologies and mechanisms to design new nanostructures of polymers and NPs, aiming to enhance the understanding of this rapidly evolving field. 

We report the use of fluorinated polymer zwitterions to build hybrid systems for efficient CO₂electroreduction. 

We report a new design of polymer phenylacetylene (PA) ligands and the ligand exchange methodology for colloidal noble metal nanoparticles (NPs). PA-terminated poly(ethylene glycol) (PEG) can bind to metal NPs through acetylide (M-CC-R) that affords a high grafting density. The ligand−metal interaction can be switched between σ bonding and extended π backbonding by changing grafting conditions. The σ bonding of PEG−PA with NPs is strong and it can compete with other capping ligands including thiols, while the π backbonding is much weaker. The σ bonding is also demonstrated to improve the catalytic performance of Pd for ethanol oxidation and prevent surface absorption of the reaction intermediates. Those unique binding characteristics will enrich the toolbox in the control of colloidal surface chemistry and their applications using polymer ligands. 

We report a facile method to prepare polymer-grafted plasmonic metal nanoparticles (NPs) that exhibit pH-responsive surface-enhanced Raman scattering (SERS). The concept is based on the use of pH- responsive polymers, such as poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH), as multi- dentate ligands to wrap around the surface of NPs instead of forming polymer brushes. Upon changing the solvent quality, the grafted pH-responsive polymers would drive reversible aggregation of NPs, leading to a decreased interparticle distance. This creates numerous hot spots, resulting in a secondary enhancement of SERS as compared to the SERS from discrete NPs. For negatively charged PAA-grafted NPs, the SERS response at pH 2.5 showed a secondary enhancement of up to 104-fold as compared to the response for discrete NPs at pH 12. Similarly, positively charged PAH-grafted AuNPs showed an oppo- site response to pH. We demonstrated that enhanced SERS with thiol-containing and charged molecular probes was indeed from the pH-driven solubility change of polymer ligands. Our method is different from the conventional SERS sensors in the solid state. With pH-responsive polymer-grafted NPs, SERS can be performed in solution with high reproducibility and sensitivity but without the need for sample pre-con- centration. These findings could pave the way for innovative designs of polymer ligands for metal NPs where polymer ligands do not compromise interparticle plasmon coupling.