The biggest challenge of exploring the catalytic properties of under-coordinated nanoclusters is the issue of stability. We demonstrate herein that chemical dopants on sulfur-doped graphene (S-G) can be utilized to stabilize ultrafine (sub-2 nm) Au<sub>25</sub>(PET)18 clusters to enable stable nitrogen reduction reaction (NRR) without significant structural degradation. The Au<sub>25</sub>@S-G exhibits an ammonia yield rate of 27.5μgNH<sub>3</sub> ∙ mg<sub>Au</sub><sup>-1</sup> ∙ h<sup>-1</sup> at -0.5 V with faradic efficiency of 2.3%. More importantly, the anchored clusters preserve ~ 80% NRR activity after four days of continuous operation, a significant improvement over the 15% remaining ammonia production rate for clusters loaded on undoped graphene tested under the same conditions. Isotope labeling experiments confirmed the ammonia was a direct reaction product of N<sub>2</sub> feeding gas instead of other chemical contaminations. Ex-situ X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy of post-reaction catalysts reveal that the sulfur dopant plays a critical role in stabilizing the chemical state and coordination environment of Au atoms in clusters. Further ReaxFF molecular dynamics (RMD) simulation confirmed the strong interaction between Au nanoclusters (NCs) and S-G. Furthermore, this substrate-anchoring process could serve as an effective strategy to study ultrafine nanoclusters’ electrocatalytic behavior while minimizing the destruction of the under-coordinated surface motif under harsh electrochemical reaction conditions.
Simplified procedures are presented for the analysis of the fundamental vibration mode response of concrete gravity dam systems for two special cases: (a) Dams with reservoirs of impounded water supported on rigid foundation rock; and (b) dams with empty reservoirs supported on flexible foundation rock. In the first case, the effects of dam‐water interaction and reservoir bottom absorption on dam response are included, whereas the effects of dam‐foundation rock interaction are included in the second case. In each case, the response of the fundamental vibration mode of a dam monolith is modeled by an equivalent single degree‐of‐freedom system with frequency‐independent properties chosen to represent the effects of complicated, frequency‐dependent hydrodynamic terms or foundation‐rock flexibility terms, as appropriate. The maximum earthquake‐induced deformations and equivalent lateral forces can be computed using the response spectrum for a specified ground motion. The procedures and results presented in this paper are extended in a companion paper to develop a simplified analytical procedure for concrete gravity dams that includes the simultaneous effects of dam‐water interaction, reservoir bottom absorption, and dam‐foundation rock interaction.
Photosynthetic biohybrid systems (PBSs) combine the strengths of inorganic materials and biological catalysts by exploiting semiconductor broadband light absorption to capture solar energy and subsequently transform it into valuable CO2-derived chemicals by taking advantage of the metabolic pathways in living organisms. In this work, we first traverse through a brief history of recent PBSs, demonstrating the modularity and diversity of possible architectures to rival and, in many cases, surpass the performance of chemistry or biology alone before envisioning the future of these hybrid systems, opportunities for improvement, and its role in sustainable living here on earth and beyond.
With few exceptions, most of the hominid evolutionary record in Africa is closely associated with the East African Rift System. The exceptions are the South African and Chadian hominids collected from the southern and west‐central parts of the continent, respectively Ethiopia's Middle Awash region stands alone as the most prolific paleo‐anthropological area ever discovered (Figure 1). Its paleontological record has yielded over 13,000 vertebrate fossils, including several hominid taxa, ranging in age from 5.8 Ma to the present. The uniqueness of the Middle Awash hominid sites lies in their occurrence within long, > 6 Ma volcanic and sedimentary stratigraphic records.
Abstract Various alkynyltrimethylsilanes and aryldiazonium tetrafluoroborates react under the optimized conditions to afford a series of diaryl or aryl—alkyl acetylenes as the desired coupling products.
Abstract The inelastic response of one‐storey, asymmetric‐plan systems to two excitations is presented and analysed with the objective of identifying the influence of system parameters: uncoupled lateral vibration period, uncoupled torsional‐to‐lateral frequency ratio, stiffness eccentricity, relative values of the strength and stiffness eccentricities, and yield factor. Furthermore, the influence of yielding on the response of asymmetric‐plan systems is examined. In particular, we determine whether the well known relationship between the response of yielding and elastic single‐degree‐of‐freedom (SDF) systems is also applicable to asymmetric‐plan systems.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.