An innovative type of lithium decahydroborate (Li@B(10)H(14)) complex with a basketlike complexant of decaborane (B(10)H(14)) has been designed using quantum mechanical methods. As Li atom binds in a handle fashion to terminal electrophilic boron atoms of the decaborane basket, its NBO charge q (Li) is found to be 0.876, close to +1. This shows that the Li atom has been ionized to form a cation and an anion at the open end of B(10)H(14). The most fascinating feature of this Li doping is its loosely bound valence electron, which has been pulled into the cavity of the B(10)H(14) basket and become diffuse by the electron-deficient morphological features of the open end of the B(10)H(14) basket. Strikingly, the first hyperpolarizability (beta(0)) of Li@B(10)H(14) is about 340 times larger than that of B(10)H(14), computed to be 23,075 au (199 x 10(-30) esu) and 68 au, respectively. Besides this, the intercalation of the Li atom to the B(10)H(14) basket brings some distinctive changes in its Raman, (11)B NMR, and UV-vis spectra along with its other electronic properties that might be used by the experimentalists to identify this novel kind of Li@B(10)H(14) complex with a large electro-optical response. This study may evoke the possibility to explore a new thriving area, i.e., alkali metal-boranes for NLO application.

The photocatalytic reduction of CO2 to energy carriers has emerged as one of the most promising strategies to alleviate the energy crisis and CO2 pollution, for which the development of catalyst was considered as the determining factor for the accomplishment of this conversion process. In this study, three stable and isostructural metal–organic frameworks (denoted as MOF-Ni, MOF-Co, and MOF-Cu) have been synthesized and used as heterogeneous catalysts in photocatalytic CO2 reduction reaction (CO2RR). It is worth noting that the MOF-Ni exhibited very high selectivity of 97.7% for photoreducing CO2 to CO, which has exceeded most of the reported MOF-based catalysts in the field. Significantly, the MOFs associated with a monometallic catalytic center offer a simple and precise structural model which allows us to understand more definitively the specific effects of different metal-ion species on photoreduction of CO2 as well as the reactive mechanism.

Efficient conversion of carbon dioxide (CO2) into value-added products is essential for clean energy research. Design of stable, selective, and powerful electrocatalysts for CO2 reduction reaction (CO2RR) is highly desirable yet largely unmet. In this work, a series of metalloporphyrin-tetrathiafulvalene based covalent organic frameworks (M-TTCOFs) are designed. Tetrathiafulvalene, serving as electron donator or carrier, can construct an oriented electron transmission pathway with metalloporphyrin. Thus-obtained M-TTCOFs can serve as electrocatalysts with high FECO (91.3%, −0.7 V) and possess high cycling stability (>40 h). In addition, after exfoliation, the FECO value of Co-TTCOF nanosheets (~5 nm) is higher than 90% in a wide potential range from −0.6 to −0.9 V and the maximum FECO can reach up to almost 100% (99.7%, −0.8 V). The electrocatalytic CO2RR mechanisms are discussed and revealed by density functional theory calculations. This work paves a new way in exploring porous crystalline materials in electrocatalytic CO2RR.

Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen.

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