The room‐temperature nitrogen reduction reaction (NRR) is of paramount significance for both the fertilizer industry and fundamental catalysis science. To produce ammonia from water, air, and sunlight, the photocatalytic NRR is targeted to significantly release the energy and environmental pressure associated with the current Habor–Bosch process. In this context, herein, the knowledge‐driven design of boron‐doped TiO2 is demonstrated as a photocatalyst for the nitrogen reduction reaction. Among 54 catalysts in the reported library, anatase TiO2(101) modified by boron doping is identified as an exceptional NRR catalyst with strong visible‐light absorption (bandgap 1.92 eV) and excellent reactivity with a small thermodynamic barrier (0.44 eV) as well as a high turnover frequency (1.08 × 10−5 s−1 site−1). Experimentally, the predictions of this work are validated using a B‐doped TiO2 nanosheet, achieving ammonia production with a yield of 3.35 mg h−1 g−1 under simulated sunlight irradiation, which significantly renews the performance record for Ti‐based photocatalyst for the NRR. This work highlights the importance of dual active site catalysts for nitrogen activation and reduction and demonstrates the capacity of knowledge‐driven catalyst design.
All of the AB_{2} Laves phases discovered so far satisfy the general crystalline structure characteristic of translational symmetry; however, we report here a new structured Laves phase directly precipitated in an aged Mg-In-Ca alloy by using aberration-corrected scanning transmission electron microscopy. The nanoprecipitate is determined to be a (Mg,In)_{2}Ca phase, which has a C14 Laves structure (hcp, space group: P6_{3}/mmc, a=6.25 Å, c=10.31 Å) but without any translational symmetry on the (0001)_{p} basal plane. The (Mg,In)_{2}Ca Laves phase contains two separate unit cells promoting the formation of five tiling patterns. The bonding of these patterns leads to the generation of the present Laves phase, followed by the Penrose geometrical rule. The orientation relationship between the Laves precipitate and Mg matrix is (0001)_{p}//(0001)_{α} and [11[over ¯]00]_{p}//[112[over ¯]0]_{α}. More specifically, in contrast to the traditional view that the third element would orderly replace other atoms in a manner of layer by layer on the close-packed (0001)_{L} plane, the In atoms here have orderly occupied certain position of Mg atomic columns along the [0001]_{L} zone axis. The finding would be interesting and important for understanding the formation mechanism of Laves phases, and even atom stacking behavior in condensed matter.
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