Efficient production of ammonia using environmentally friendly techniques under ambient conditions is crucial to renewable energy storage and industrial applications, and catalysts with new reaction pathways are highly desirable. In this work, black phosphorus (BP) is used as a metal‐free 2D catalyst for the photoelectrochemical (PEC) nitrogen reduction reaction (NRR). The electrode is fabricated by layer‐by‐layer assembly of BP nanosheets on an indium tin oxide substrate. The PEC NRR activity in the N2 saturated aqueous electrolyte without a sacrificial agent is excellent, as exemplified by an ammonia yield rate of 102.4 µg h−1 mgcat.−1 and Faradaic efficiency of 23.3% at −0.4 V, which are the best among nonmetal catalysts for synthesis of ammonia by photocatalysis and electrocatalysis. Furthermore, the BP electrode shows excellent stability after 6 consecutive cycles. The excellent PEC catalytic properties are attributed to the light excitation enhanced electrocatalytic process and that the external bias promoted photocatalytic process improves ammonia production synergistically. The results not only demonstrate the great potential of BP in PEC catalysis, but also identify a promising technique to produce ammonia under ambient conditions using solar energy and electric energy.

Two dimensional (2D) nanoribbons constitute an emerging nanoarchitecture for advanced microelectronics and energy conversion due to the stronger size confinement effects compared to traditional nanosheets. Triclinic crystalline red phosphorus (cRP) composed by a layered structure is a promising 2D phosphorus allotrope and the tube‐like substructure is beneficial to the construction of nanoribbons. In this work, few‐layer cRP nanoribbons are synthesized and the effectiveness in the electrochemical nitrogen reduction reaction (NRR) is investigated. An iodine‐assisted chemical vapor transport (CVT) method is developed to synthesize circa 10 g of bulk cRP lumps with a yield of over 99 %. With the aid of probe ultrasonic treatment, high‐quality cRP microcrystals are exfoliated into few‐layer nanoribbons (cRP NRs) with large aspect ratios. As non‐metallic materials, cRP NRs are suitable for the electrochemical nitrogen reduction reaction. The ammonia yield is 15.4 μg h−1 mgcat.−1 at −0.4 V vs. reversible hydrogen electrode in a neutral electrolyte under ambient conditions and the Faradaic efficiency is 9.4 % at −0.2 V. Not only is cRP a promising catalyst, but also the novel strategy expands the application of phosphorus‐based 2D structures beyond that of traditional nanosheets.

A series of dimethylaluminum complexes (L1a–i)AlMe2 (2a–i, where HL1a–i = 2-(2′-ArNH)phenyl-4-R1-oxazoline) bearing chiral, bidentate anilido-oxazolinate ligands have been prepared and characterized. Six of the complexes, in the presence of an alcohol cocatalyst, are shown to be active initiators for the stereoselective ring-opening polymerization of rac-lactide in toluene solution and under bulk conditions, yielding polylactides with a range of tacticity from slightly isotactic to moderately heterotactic. The reactivity and selectivity of these catalysts are discussed on the basis of the effect of their substituents.

Development of efficient catalysts for ammonia production under ambient conditions is a challenge. In this work, edge-rich black phosphorus nanoflakes (eBP NFs) are synthesized for highly efficient photocatalytic nitrogen fixation. The eBP NFs synthesized by a chemical etching exfoliation method have a uniform size and about 90 nm wide and the flake-like structure is enshrouded with crystal-domain edges. Without using any cocatalysts, the eBP NFs catalyze nitrogen fixation at a rate of 2.37 mmol·h–1·g–1 under visible-light irradiation. The photocatalytic process is analyzed by photoelectrochemical and transient absorption measurements, which disclose electron transfer from eBP NFs to N2 for subsequent hydrogenation. Besides the facile and scalable synthesis method, eBP NFs with a high photocatalytic nitrogen fixation efficiency have great potential in ammonia production.

Recently, polycarbonates have attracted considerable research interest because of their potential biodegradability and sustainability. Here, we present a direct route for the synthesis of polycarbonates and poly(ether carbonate)s from carbon dioxide (CO 2 ) and diols, promoted by Cs 2 CO 3 and CH 2 Cl 2 under 1 atm of CO 2 . Quantitative conversion of diols and polymers with up to 11 kg/mol molecular weight could be obtained. While benzylic diols lead to predominantly carbonate linkage, aliphatic diols result in the incorporation of the methylene unit of CH 2 Cl 2 that produces poly(ether carbonate)s. Both primary and secondary diols have been successfully incorporated into the polymer chain.

Hydrosilylation catalyzed by a high-valent nitridoruthenium(VI) compound, [RuN(saldach)(CH3OH)]+[ClO4]− (1, where saldach is the dianion of racemic N,N′-cyclohexan-diyl-bis(salicylideneimine)) is described. Using phenylsilane as reductant, a variety of unsaturated organic substrates, including aldehydes, ketones, and imines, are effectively reduced to alcohols and amines, respectively, accompanied by the redistribution of PhSiH3 at silicon. Mechanistic studies indicate that the catalysis proceeds via silane activation rather than carbonyl activation, and the silane is likely activated via multiple pathways, including a radical-based pathway.

Black phosphorus (BP) is developed as a highly efficient metal‐free photoelectrochemical (PEC) ammonia synthesis catalyst for the first time. In article number 2002731, Jiahong Wang, Xue‐Feng Yu, and co‐workers report an ammonia yield rate as high as 102.4 μg h−1 mgcat·−1. The excellent catalytic properties identify a promising technique to produce ammonia under ambient conditions using solar energy and electric energy.

A family of new chiral C2 symmetric amido‐oxazolinate ligands H2L (1 a‐1 d) that are bridged by three different linkers based on m‐phenylenediamine, 4‐(4’‐aminobenzyl)benzenamine, and 1,8‐diaminoanthracene have been synthesized in high yields (85‐90 %). Treatment of ligands (1 a‐1 d) with two equiv. of Zn[N(SiMe3)2]2 in dry toluene generated a series of heteroleptic dizinc complexes (L)[ZnN(SiMe3)2]2 (2 a‐2 d) and reaction of 1 b with one equiv. of Zn[N(SiMe3)2]2 leads to formation of a homoleptic binuclear zinc complex (L)2Zn2 (3 b) in good yield. Complexes 2 a‐2 d were found to be effective catalysts for asymmetric alternating copolymerization of CO2 and cyclohexene oxide (CHO). The catalyst 2 a is more active towards polycarbonate formation (78 % carbonate linkages), while the catalyst 2 d generates highly isotactic poly(cyclohexene carbonate) (86 % of m‐centered tetrads).