Porous nonprecious metal-based nanomaterials have gained considerable attention in heterogeneous catalysis owing to their low price, high specific surface area, efficient mass/electron transfer, tunable pore structure, and unique physicochemical properties. Controlling the phase and compositions of these porous nonprecious metal-based materials is critical to their applications. Porous nonprecious transition-metal borides (TMBs), typical metal−metalloid alloys, have recently received much interest because of their optimized electronic structure, adjustable crystal phase, and abundant active site. The controlled tuning of the porous structure of TMBs, exploring the relationship between the structure and performance, and understanding the function of B are essential for developing catalysts with excellent performance; however, these factors have rarely been reviewed. Herein, a detailed summary of the synthesis methods of porous TMBs is provided by precisely defining their shape, composition, and pore size/structure. Incorporating B into metals can significantly alter their performance due to the unique metalloid properties of B. Further, we focus on the key roles of B in porous TMBs for related heterogeneous catalytic applications, including phase control, regulated electronic structure, optimized adsorption of reaction intermediates, and enhanced charge transfer and stability. Finally, we outline the shortcomings, challenges, and possible development of porous TMBs, which need to be further explored to increase TMBs' contribution to heterogeneous catalyst applications and beyond.

New experimental procedures for the preparation of dibenziodolium salts by oxidative cyclization of 2-iodobiphenyl in the presence of appropriate strong acids are described. Particularly useful is a convenient one-pot synthesis of dibenziodolium hydrogen sulfate from 2-iodobiphenyl using Oxone as an inexpensive and environmentally safe oxidant. Dibenziodolium hydrogen sulfate, bis(triflyl)imidate, or triflate can be readily converted to various other dibenziodolium derivatives (chloride, bromide, thiocyanate, azide, cyanide, phenylsulfinate) by anion exchange. Structures of key products have been established by single-crystal X-ray diffraction analysis. Particularly interesting is the X-ray structure of dibenziodolium thiocyanate, which represents the first example of a structurally characterized hypervalent iodine compound with a relatively short iodine-sulfur secondary bond distance.

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The first method of plasmon-induced nitroxide-mediated polymerization on periodical gold gratings has been developed.

This article reviews recent fabrication methods for surface‐enhanced Raman spectroscopy (SERS) substrates with a focus on advanced nanoarchitecture based on noble metals with special nanospaces (round tips, gaps, and porous spaces), nanolayered 2D materials, including hybridization with metallic nanostructures (NSs), and the contemporary repertoire of nanoarchitecturing with organic molecules. The use of SERS for multidisciplinary applications has been extensively investigated because the considerably enhanced signal intensity enables the detection of a very small number of molecules with molecular fingerprints. Nanoarchitecture strategies for the design of new NSs play a vital role in developing SERS substrates. In this review, recent achievements with respect to the special morphology of metallic NSs are discussed, and future directions are outlined for the development of available NSs with reproducible preparation and well‐controlled nanoarchitecture. Nanolayered 2D materials are proposed for SERS applications as an alternative to the noble metals. The modern solutions to existing limitations for their applications are described together with the state‐of‐the‐art in bio/environmental SERS sensing using 2D materials‐based composites. To complement the existing toolbox of plasmonic inorganic NSs, hybridization with organic molecules is proposed to improve the stability of NSs and selectivity of SERS sensing by hybridizing with small or large organic molecules.

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Plasmon-assisted transformations of organic compounds represent a novel opportunity for conversion of light to chemical energy at room temperature. However, the mechanistic insights of interaction between plasmon energy and organic molecules is still under debate. Herein, we proposed a comprehensive study of the plasmon-assisted reaction mechanism using unsymmetric iodonium salts (ISs) as an organic probe. The experimental and theoretical analysis allow to exclude the possible thermal effect or hot electron transfer. We found that plasmon interaction with unsymmetrical ISs led to the intramolecular excitation of electron followed by the regioselective cleavage of C-I bond with the formation of electron-rich radical species, which cannot be explained by the hot electron excitation or thermal effects. The high regioselectivity is explained by the direct excitation of electron to LUMO with the formation of dissociative excited state according to quantum-chemical modeling, which provide a novel opportunities to the fine control of reactivity using plasmon energy.