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The surface frustrated Lewis pairs (SFLPs) open up new opportunities for substituting noble metals in the activation and conversion of stable molecules. However, the applications of SFLPs on a larger scale are impeded by the complex construction process, low surface density, and sensitivity to the reaction environment. Herein, wurtzite‐structured crystals such as GaN, ZnO, and AlP are found for developing natural, dense, and stable SFLPs. It is revealed that the SFLPs can naturally exist on the (100) and (110) surfaces of wurtzite‐structured crystals. All the surface cations and anions serve as the Lewis acid and Lewis base in SFLPs, respectively, contributing to the surface density of SFLPs as high as 7.26×1014 cm−2. Ab initio molecular dynamics simulations indicate that the SFLPs can keep stable under high temperatures and the reaction atmospheres of CO and H2O. Moreover, outstanding performance for activating the given small molecules is achieved on these natural SFLPs, which originates from the optimal orbital overlap between SFLPs and small molecules. Overall, these findings not only provide a simple method to obtain dense and stable SFLPs but also unfold the nature of SFLPs toward the facile activation of small molecules. [ABSTRACT FROM AUTHOR]

The rapid release of gas by a chemical reaction to generate momentum is one of the most fundamental ways to elicit motion that could be used to sustain and control the motility of objects. We report that hollow crystals of a three‐dimensional supramolecular metal complex that releases gas by photolysis can propel themselves or other objects and advance in space when suspended in mother solution. In needle‐like regular crystals, the reaction occurs mainly on the surface and results in the formation of cracks that evolve due to internal pressure; the expansion on the cracked surface of the crystal results in bending, twisting, or coiling of the crystal. In hollow crystals, gas accumulates inside their cavities and emanates preferentially from the recess at the crystal terminus, propelling the crystals to undergo directional photomechanical motion through the mother solution. The motility of the object which can be controlled externally to perform work delineates the concept of "crystal microbots", realized by photoreactive organic crystals capable of prolonged directional motion for actuation or delivery. Within the prospects, we envisage the development of a plethora of light‐weight, efficient, autonomously operating robots based on organic crystals with high work capacity where motion over large distances can be attained due to the large volume of latent gas generated from a small volume of the crystalline solid. [ABSTRACT FROM AUTHOR]

Dendrites growth and unstable interfacial Li+ transport hinder the practical application of lithium metal batteries (LMBs). Herein, we report an active layer of 2,4,6–trihydroxy benzene sulfonyl fluorine on copper substrate that induces oriented Li+ deposition and generates highly crystalline solid‐electrolyte interphase (SEI) to achieve high‐performance LMBs. The lithiophilic −SO2− groups of highly crystalline SEI accept the rapidly transported Li+ ions and form a dense inner layer of LiF and Li3N, which regulate Li+ plating morphology along the (110) crystal surface toward dendrite‐free Li anode. Thus, Li||Cu cells with lithiophilic SEI achieve an average deposition efficiency of 99.8 % after 700 cycles, and Li||Li cells operate well for 1100 h. Besides, Li||LiNi0.8Co0.1Mn0.1O2 cells with modified SEI exhibit a capacity retention that is 14 times than that of conventional SEI. Even at −60 °C, Li||Cu cells reach stable deposition efficiency of 83.2 % after 100 cycles. [ABSTRACT FROM AUTHOR]

Precisely introducing topological defects is an important strategy in nanographene crystal engineering because defects can tune π‐electronic structures and control molecular assemblies. The synergistic control of the synthesis and assembly of nanographenes by embedding the topological defects to afford two‐dimensional (2D) crystals on surfaces is still a great challenge. By in‐situ embedding ladder bipyrazinylene (LBPy) into acene, the narrowest nanographene with zigzag edges, we have achieved the precise preparation of 2D nonbenzenoid heteroacene crystals on Au(111). Through intramolecular electrocyclization of o‐diisocyanides and Au adatom‐directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and lead to the molecular 2D assembly via LBPy‐derived interlocking hydrogen bonds. Using bond‐resolved scanning tunneling microscopy, we determined the atomic structures of the nonbenzenoid heteroacene product and diverse organometallic intermediates. The tunneling spectroscopy measurements revealed the electronic structure of the nonbenzenoid heteroacene, which is supported by density functional theory (DFT) calculations. The observed distinct organometallic intermediates during progression annealing combined with DFT calculations demonstrated that LBPy formation proceeds via electrocyclization of o‐diisocyanides, trapping of heteroarynes by Au adatoms, and stepwise elimination of Au adatoms. [ABSTRACT FROM AUTHOR]

Metal halide perovskite single crystals are promising for diverse optoelectronic applications. As a universal issue of solution‐grown perovskite single crystals, surface contamination causes adverse effect on material properties and device performance. Herein, learning from the self‐cleaning effect of lotus leaf, we address the surface contamination issue by introducing an amphiphilic long‐chain organic amine into the perovskite crystal growth solution. Self‐assembly of CTAC provides a hydrophobic crystal surface, inducing spontaneous removal of residual growth solution, which results in clean surface and better optoelectronic properties of perovskite single crystals. An impressive efficiency of 23.4 % is obtained, setting a new record for FAxMA1‐xPbI3 single‐crystal perovskite solar cells (PSCs). Moreover, our strategy also applies to perovskite single crystals with different morphology and composition, which may contribute to improvement of other single‐crystal perovskite optoelectronic devices. [ABSTRACT FROM AUTHOR]

We report a photochemical bismuth vanadate (BiVO4) sensing material, which possesses a large proportion of (110) and (011) facets combined with the additional (111) facets, for the selective detection of ultra‐low concentration hydrogen sulfide (H2S) driven by visible light. Specifically, the obtained octadecahedron BiVO4 (Octa‐BiVO4) performs a high response value (67) and short response time (47.4 s) to 100 ppm H2S with good stability for nearly 100 days, as well as undisturbedness by moist air. With the combination of experimental and theoretical calculation results, the adsorption and carrier transfer behaviors of H2S molecules on the Octa‐BiVO4 crystal surface are investigated. By adjusting the ratio of different crystal facets and controlling the facets with characteristic adsorption, we achieve improved anisotropic photoinduced carrier separation and high selectivity for a specific gas. Furthermore, this facial facet engineering can be extended to the synthesis of other sensing materials, offering huge opportunities for fundamental research and technological applications. [ABSTRACT FROM AUTHOR]

Achieving predictable and programmable two‐dimensional (2D) structures with specific functions from exclusively organic soft materials remains a scientific challenge. This article unravels stereocomplex crystallization‐driven self‐assembly as a facile method for producing thermally robust discrete 2D‐platelets of diamond shape from biodegradable semicrystalline polylactide (PLA) scaffolds. The method involves co‐assembling two PLA stereoisomers, namely, PY‐PDLA and NMI‐PLLA, which form stereocomplex (SC)‐crystals in isopropanol. By conjugating a well‐known Förster resonance energy transfer (FRET) donor and acceptor dye, namely, pyrene (PY) and naphthalene monoimide (NMI), respectively, to the chain termini of these two interacting stereoisomers, a thermally robust FRET process can be stimulated from the 2D array of the co‐assembled dyes on the thermally resilient SC‐PLA crystal surfaces. Uniquely, by decorating the surface of the SC‐PLA crystals with an externally immobilized guest dye, Rhodamine‐B, similar diamond‐shaped structures could be produced that exhibit pure white‐light emission through a surface‐induced two‐step cascade energy transfer process. The FRET response in these systems displays remarkable dependence on the intrinsic crystalline packing, which could be modulated by the chirality of the co‐assembling PLA chains. This is supported by comparing the properties of similar 2D platelets generated from two homochiral PLLAs (PY‐PLLA and NMI‐PLLA) labeled with the same FRET pair. [ABSTRACT FROM AUTHOR]

Single crystal surfaces with highly coordinated sites very often hold high specific activities toward oxygen reduction reaction (ORR) and others. Transposing their high specific activity to practical high‐surface‐area electrocatalysts remains challenging. Here, ultrathin Pt(100) alloy surface is constructed via epitaxial growth. The surface shows 3.1–6.9 % compressive strain and bulk‐like characteristics as demonstrated by site‐probe reactions and different spectroscopies. Its ORR activity exceeds that of bulk Pt3Ni(100) and Pt(111) and presents a 19‐fold increase in specific activity and a 13‐fold increase in mass activity relative to commercial Pt/C. Moreover, the electrochemically active surface area (ECSA) is increased by 4‐fold compared to traditional thin films (e.g. NSTF), which makes the catalyst more tolerant to voltage loss at high current densities under fuel cell operation. This work broadens the family of extended surface catalysts and highlights the knowledge‐driven approach in the development of advanced electrocatalysts. [ABSTRACT FROM AUTHOR]

Photomechanical molecular crystals are promising materials for photon‐powered artificial actuators. To interpret the photomechanical responses, the spatiotemporal distribution of photoproducts in crystals could be an important role in addition to molecular structures, molecular packings, illumination conditions, crystal morphology, crystal size, and so on. In this study, we have found that single crystals of 2,5‐distyrylpyrazine show a smooth single‐crystal‐to‐single‐crystal photomechanical expansion, and the photochemical reaction propagates from the edge to the center of the single crystal. We revealed that the surface effect (special reactivity at the crystal surface) in addition to the cooperative effect (the reaction is facilitated by neighboring molecules) is essential for the edge‐to‐center propagation of the photochemical reaction. Our results would provide a foundation for future studies of the photochemical reaction dynamics in photomechanical molecular crystals. [ABSTRACT FROM AUTHOR]

Designing zeolite catalysts with improved mass transport properties is crucial for restrictive networks of either one‐ or two‐dimensional pore topologies. Here, we demonstrate the synthesis of finned ferrierite (FER), a commercial zeolite with two‐dimensional pores, where protrusions on crystal surfaces behave as pseudo nanoparticles. Catalytic tests of 1‐butene isomerization reveal a 3‐fold enhancement of catalyst lifetime and an increase of 12 % selectivity to isobutene for finned samples compared to corresponding seeds. Electron tomography was used to confirm the identical crystallographic registry of fins and seeds. Time‐resolved titration of Brønsted acid sites confirmed the improved mass transport properties of finned ferrierite compared to conventional analogues. These findings highlight the advantages of introducing fins through facile and tunable post‐synthesis modification to impart material properties that are otherwise unattainable by conventional synthesis methods. [ABSTRACT FROM AUTHOR]

Quartz crystal microbalance (QCM) is one of the powerful tools for the studies of molecular recognition and chiral discrimination. Its efficiency mainly relies on the design of the functional sensitive layer on the electrode surface. However, the organic sensitive layer may easily cause dissipation of oscillation or detachment and weaken the signal transfer during the molecular recognition processes. In this work, we reveal for the first time that the bare metal surface without the organic selector layer has the capability for chiral recognition in the QCM system. During the adsorption of various chiral amino acids, relatively higher selectivity of D‐enantiomers on gold (Au) surface was shown by the QCM detection. Based on analyses of the surface crystalline structure and density functional theory calculations, we demonstrate that the chiral nature of Au surface plays an important role in the selective binding of specific D‐amino acids. These results may open new insights on chiral detection by QCM system. It will also promote the construction of novel chiral sensing systems with both efficient detection and separation capability. [ABSTRACT FROM AUTHOR]