Ultrastable Atomic Copper Nanosheets for Selective Electrochemical Reduction of Carbon Dioxide

金属铜表面很容易被空气氧化，因此铜纳米材料在空气中极不稳定，如何制备原子级厚度的二维铜纳米片一直是纳米材料领域的一个挑战性难题。厦门大学化学化工学院郑南峰教授课题组发展了一种制备稳定超薄二维铜基纳米材料的有效方法，并将这类材料应用于二氧化碳的选择性电催化还原。该项研究还发现所合成的复合纳米材料能够将二氧化碳和水选择性地电化学还原为组成可调的合成气（一氧化碳和氢气混合气），在较低的还原电位下可高选择性地将二氧化碳还原成一氧化碳(其法拉第效率高达92%)。铜基纳米材料在二氧化碳电化学还原中具有优异的性能，但产物异常多样，选择性控制的难度很大。该项工作利用简单的表面配位修饰大幅改善电催化选择性的策略为二氧化碳还原电催化剂的设计提供了新思路。 该工作是在郑南峰教授指导下，并与傅钢教授课题组、加拿大Dalhousie大学张鹏教授合作完成，第一作者为化学化工学院博士生代磊，硕士生钦青、博士生汪佩、赵小静等参与了该工作。【Abstract】The electrochemical conversion of CO2 and H2O into syngas using renewably generated electricity is an attractive approach to simultaneously achieve chemical fixation of CO2 and storage of renewable energy. Developing cost-effective catalysts for selective electroreduction of CO2 into CO is essential to the practical applications of the approach. We report a simple synthetic strategy for the preparation of ultrathin Cu/Ni(OH)2 nanosheets as an excellent cost-effective catalyst for the electrochemical conversion of CO2 and H2O into tunable syngas under low overpotentials. These hybrid nanosheets with Cu(0)-enriched surface behave like noble metal nanocatalysts in both air stability and catalysis. Uniquely, Cu(0) within the nanosheets is stable against air oxidation for months because of the presence of formate on their surface. With the presence of atomically thick ultrastable Cu nanosheets, the hybrid Cu/Ni(OH)2 nanosheets display both excellent activity and selectivity in the electroreduction of CO2 to CO. At a low overpotential of 0.39 V, the nanosheets provide a current density of 4.3 mA/cm2 with a CO faradaic efficiency of 92%. No decay in the current is observed for more than 22 hours. The catalysts developed in this work are promising for building low-cost CO2 electrolyzers to produce CO.We thank the beamline BL14W1 (Shanghai Synchrotron Radiation Facility) for providing the beam time. the Ministry of Science and Technology of China (2017YFA0207302 and 2015CB93230)and the National Natural Science Foundation of China (21731005, 21420102001, 21333008). 研究工作得到了科技部和国家自然科学基金委的资助，X-射线吸收光谱测试在上海光源BL14W1线站完成

Photochemical route for synthesizing atomically dispersed palladium catalysts

该工作由校内外多个课题组共同努力，历时三年多完成。我校郑南峰、傅钢等课题组紧密协作负责催化剂的合成、表征、催化测试及机理研究；中科院物理研究所谷林研究员主要负责催化剂的球差校正透射电子显微研究；加拿大达尔豪斯大学的张鹏课题组参与催化剂的同步辐射X-射线吸收谱研究。该研究工作的第一、二作者刘朋昕、赵云均为我校博士生。【Abstract】Atomically dispersed noble metal catalysts often exhibit high catalytic performances, but the metal loading density must be kept low (usually below 0.5%) to avoid the formation of metal nanoparticles through sintering. We report a photochemical strategy to fabricate a stable atomically dispersed palladium–titanium oxide catalyst (Pd 1 /TiO2 ) on ethylene glycolate (EG)–stabilized ultrathin TiO2 nanosheets containing Pd up to 1.5%.The Pd 1 /TiO2 catalyst exhibited high catalytic activity in hydrogenation of C=C bonds, exceeding that of surface Pd atoms on commercial Pd catalysts by a factor of 9.No decay in the activity was observed for 20 cycles. More important, the Pd 1 /TiO2 -EG system could activate H2 in a heterolytic pathway, leading to a catalytic enhancement in hydrogenation of aldehydes by a factor of more than 55.Supported by Ministry of Science and Technology of China grant 2015CB932303; National Natural Science Foundation of China grants 21420102001, 21131005, 21390390, 21133004, 21373167, 21573178, and 21333008; a NSERC CGS Alexander Graham Bell scholarship (D.M.C.); and a NSERC Discovery grant (P.Z.)

CB‐HRNet: A Class‐Balanced High‐Resolution Network for the evaluation of endoscopic activity in patients with ulcerative colitis

Abstract Endoscopic evaluation is the key to the management of ulcerative colitis (UC). However, there is interobserver variability in interpreting endoscopic images among gastroenterologists. Furthermore, it is time‐consuming. Convolutional neural networks (CNNs) can help overcome these obstacles and has yielded preliminary positive results. We aimed to develop a new CNN‐based algorithm to improve the performance for evaluation tasks of endoscopic images in patients with UC. A total of 12,163 endoscopic images from 308 patients with UC were collected from January 2014 to December 2021. The training set and test set images were randomly divided into 37,515 and 3191 after excluding possible interference and data augmentation. Mayo Endoscopic Subscores (MES) were predicted by different CNN‐based models with different loss functions. Their performances were evaluated by several metrics. After comparing the results of different CNN‐based models with different loss functions, High‐Resolution Network with Class‐Balanced Loss achieved the best performances in all MES classification subtasks. It was especially great at determining endoscopic remission in UC, which achieved a high accuracy of 95.07% and good performances in other evaluation metrics with sensitivity 92.87%, specificity 95.41%, kappa coefficient 0.8836, positive predictive value 93.44%, negative predictive value 95.00% and area value under the receiver operating characteristic curve 0.9834, respectively. In conclusion, we proposed a new CNN‐based algorithm, Class‐Balanced High‐Resolution Network (CB‐HRNet), to evaluate endoscopic activity of UC with excellent performance. Besides, we made an open‐source dataset and it can be a new benchmark in the task of MES classification

Carbon Monoxide Promotes the Catalytic Hydrogenation on Metal Cluster Catalysts

Size effect plays a crucial role in catalytic hydrogenation. The highly dispersed ultrasmall clusters with a limited number of metal atoms are one candidate of the next generation catalysts that bridge the single-atom metal catalysts and metal nanoparticles. However, for the unfavorable electronic property and their interaction with the substrates, they usually exhibit sluggish activity. Taking advantage of the small size, their catalytic property would be mediated by surface binding species. The combination of metal cluster coordination chemistry brings new opportunity. CO poisoning is notorious for Pt group metal catalysts as the strong adsorption of CO would block the active centers. In this work, we will demonstrate that CO could serve as a promoter for the catalytic hydrogenation when ultrasmall Pd clusters are employed. By means of DFT calculations, we show that Pdn n=2‐147 clusters display sluggish activity for hydrogenation due to the too strong binding of hydrogen atom and reaction intermediates thereon, whereas introducing CO would reduce the binding energies of vicinal sites, thus enhancing the hydrogenation reaction. Experimentally, supported Pd2CO catalysts are fabricated by depositing preestablished [Pd2(μ-CO)2Cl4]2- clusters on oxides and demonstrated as an outstanding catalyst for the hydrogenation of styrene. The promoting effect of CO is further verified experimentally by removing and reintroducing a proper amount of CO on the Pd cluster catalysts

Surface Coordination of Multiple Ligands Endows N‐Heterocyclic Carbene‐Stabilized Gold Nanoclusters with High Robustness and Surface Reactivity

Deciphering the molecular pictures of the multi-component and non-periodic organic-inorganic interlayer is a grand technical challenge. Here we show that the atomic arrangement of hybrid surface ligands on metal nanoparticles can be precisely quantified through comprehensive characterization of a novel gold cluster, Au 44 ( i Pr 2 -bimy) 9 (PA) 6 Br 8 , which features three types of ligands, namely, carbene (1,3-diisopropylbenzimidazolin-2-ylidene, i Pr 2 -bimy), alkynyl (phenylacetylide, PA), and halide (Br), respectively. The delicately balanced stereochemical effects and bonding capabilities of the three ligands give rise to peculiar geometrical and electronic structures. Remarkably, despite its complex and highly distorted surface structure, Au 44 ( i Pr 2 -bimy) 9 (PA) 6 Br 8 exhibits unusual catalytic properties and yet it is highly stable, both chemically and thermally. Moreover, rich reactive sites on the cluster surface raise the prospect of bio-compatibility (as it can be functionalized to yield water-soluble derivatives) and bio-applications.peerReviewe

Microcomb-driven silicon photonic systems.

Microcombs have sparked a surge of applications over the past decade, ranging from optical communications to metrology1-4. Despite their diverse deployment, most microcomb-based systems rely on a large amount of bulky elements and equipment to fulfil their desired functions, which is complicated, expensive and power consuming. By contrast, foundry-based silicon photonics (SiPh) has had remarkable success in providing versatile functionality in a scalable and low-cost manner5-7, but its available chip-based light sources lack the capacity for parallelization, which limits the scope of SiPh applications. Here we combine these two technologies by using a power-efficient and operationally simple aluminium-gallium-arsenide-on-insulator microcomb source to drive complementary metal-oxide-semiconductor SiPh engines. We present two important chip-scale photonic systems for optical data transmission and microwave photonics, respectively. A microcomb-based integrated photonic data link is demonstrated, based on a pulse-amplitude four-level modulation scheme with a two-terabit-per-second aggregate rate, and a highly reconfigurable microwave photonic filter with a high level of integration is constructed using a time-stretch approach. Such synergy of a microcomb and SiPh integrated components is an essential step towards the next generation of fully integrated photonic systems