The ability to synthesize a broad spectrum of metal clusters (MCs) with their size controllable on a subnanometer scale presents an enticing prospect for exploring nanosize-dependent properties. Here we report an innovative design of a capping agent from a polytriazolium poly(ionic liquid) (PIL) in a vesicular form in solution that allows for crafting a variety of MCs including transition metals, noble metals, and their bimetallic alloy with precisely controlled sizes (∼1 nm) and record-high catalytic performance. The ultrastrong stabilization power is a result of an unusual synergy between the conventional binding sites in the heterocyclic cations in PIL and an in situ generated polycarbene structure induced simultaneously to the reduction reaction.

Nanoporous graphitic carbon membranes with defined chemical composition and pore architecture are novel nanomaterials that are actively pursued. Compared with easy-to-make porous carbon powders that dominate the porous carbon research and applications in energy generation/conversion and environmental remediation, porous carbon membranes are synthetically more challenging though rather appealing from an application perspective due to their structural integrity, interconnectivity and purity. Here we report a simple bottom–up approach to fabricate large-size, freestanding and porous carbon membranes that feature an unusual single-crystal-like graphitic order and hierarchical pore architecture plus favourable nitrogen doping. When loaded with cobalt nanoparticles, such carbon membranes serve as high-performance carbon-based non-noble metal electrocatalyst for overall water splitting.

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Electro‐reforming of renewable biomass resources is an alternative technology for sustainable pure H2 production. Herein, we discovered an unconventional cation effect on the concurrent formate and H2 production via glycerol electro‐reforming. In stark contrast to the cation effect via forming double layers in cathodic reactions, residual cations at the anode were discovered to interact with the glycerol oxidation intermediates to steer its product selectivity. Through a combination of product analysis, transient kinetics, crown ether trapping experiments, in situ IRRAS and DFT calculations, the aldehyde intermediates were discovered to be stabilized by the Li+ cations to favor the non‐oxidative C−C cleavage for formate production. The maximal formate efficiency could reach 81.3 % under ≈60 mA cm−2 in LiOH. This work emphasizes the significance of engineering the microenvironment at the electrode–electrolyte interface for efficient electrolytic processes.

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Capturing volatile radioactive nuclides including iodine (I129 or I131) is one of the major problems to be solved for environmental sustainability. Multiple types of functional microporous materials such as metal organic frameworks and covalent organic frameworks have been constructed for iodine emission control. However, most of the microporous materials are limited by their weak binding force with iodine and low stability, leading to low capture efficiencies. Herein, the synthesis of pyridyl conjugated microporous polymer networks with large surface areas (PCMP‐Y) up to 1304 m2 g−1 and high yields up to 95% via a simple Yamamoto cross‐coupling reaction, is reported. The PCMP‐Y carries amine and pyridine N groups which have stronger interactions with iodine molecules. The high specific surface areas and porosities of PCMP‐Y facilitate iodine capture, delivering a maximum adsorption capacity of 4.75 g g−1 in a short time (3 h), which is superior to a majority of porous materials reported. Moreover, the reversible desorption nature of PCMP‐Y capturing iodine imparts a platform for metal‐free heterogeneous catalyst, which can be applied to synthesize aminobenzothiazole medicines via O2‐promoted cascade reactions.

A balanced detection of both adsorbates and dissolved species is very important for the clarification of the electrochemical reaction mechanism yet remains a major challenge for different modes of electrochemical infrared (IR) spectroscopy. Among others, conventional attenuated total reflection-surfaceenhanced IR absorption spectroscopy (ATR-SEIRAS) is far less sensitive to low-concentration solution species than to surface species. We report herein an electrochemical wide-frequency ATR-SEIRAS with a novel thin-layer flow cell design, fulfilling the simultaneous detection of the variations of surface and solution species. This setup consists of a silicon wafer (with one side micromachined and the other side metallized), a thin-layer electrolyte structure with tunable thickness and flow rate, and a tilt-correction system based on laser collimation, enabling a well-controlled mass transport within the electrolyte layer and the spectral differentiation of solution species from adsorbates. Using acidic methanol oxidation on a Pt film electrode as a model system, besides SEIRA bands for adsorbed CO and formate intermediates, IR spectral signals for dissolved products CO 2 , formic acid, and methyl formate can be readily identified for a quiescent electrolyte layer of ∼20 μm, which are otherwise undetected with conventional ATR-SEIRAS, as indicated by the trend of spectral features with increasing thickness or flow rate.