Tuning the surface electronic structure of noble metal aerogels to promote the electrocatalytic oxygen reduction

The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts.Here,the surface electronic structure of Ptbased noble metal aerogels(NMAs)was modulated by various organic ligands,among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis.Theoretical calculations suggested the smaller energy barrier for the transformation of O^(*) to OH^(*) and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals,thus enhancing the ORR intrinsic activity.Both Pt3Ni and Pt Pd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media.Remarkably,the 4-methylphenylene modified Pt Pd aerogel exhibited the higher halfwave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C.This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.

A general synthetic strategy for N, P co-doped graphene supported metal-rich noble metal phosphides for hydrogen generation

The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.

Advances in noble metal-modified g-C3N4 heterostructures toward enhanced photocatalytic redox ability

The photocatalytic activity of catalysts depends on the energy-harvesting ability and the separation or transport of photogenerated carriers.The light absorption capacity of graphitic carbon nitride(g-C_(3)N_(4))-based composites can be enhanced by adjusting the surface plasmon resonance(SPR)of noble metal nanoparticles(e.g.,Cu,Au,and Pd)in the entire visible region.Adjustments can be carried out by varying the nanocomponents of the materials.The SPR of noble metals can enhance the local electromagnetic field and improve interband transition,and resonant energy transfer occurs from plasmonic dipoles to electron-hole pairs via near-field electromagnetic interactions.Thus,noble metals have emerged as relevant nanocomponents for g-C_(3)N_(4) used in CO_(2) photoreduction and water splitting.Herein,recent key advances in noble metals(either in single atom,cluster,or nanoparticle forms)and composite photocatalysts based on inorganic or organic nanocomponent-incorporated g-C_(3)N_(4) nanosheets are systematically discussed,including the applications of these photocatalysts,which exhibit improved photoinduced charge mobility in CO_(2) photoconversion and H2 production.Issues related to the different types of multi-nanocomponent heterostructures(involving Schottky junctions,Z-/S-scheme heterostructures,noble metals,and additional semiconductor nanocomponents)and the adjustment of dimensionality of heterostructures(by incorporating noble metal nanoplates on g-C_(3)N_(4) forming 2D/2D heterostructures)are explored.The current prospects and possible challenges of g-C_(3)N_(4) composite photocatalysts incorporated with noble metals(e.g.,Au,Pt,Pd,and Cu),particularly in water splitting,CO_(2) reduction,pollution degradation,and chemical conversion applications,are summarized.

概念、视角、叙述与古代中国墓葬美术史书写——巫鸿The Art of the Yellow Springs:Understanding Chinese Tombs评述

在大量美术考古材料不断出土的情况下,新方法、新视角以及由此衍生出的一些重要的学术概念,构成了最近30年来古代中国墓葬美术史研究的总体特征。如空间性、物质性、时间性这三个学术概念就建构了巫鸿新作《黄泉下的美术——宏观中国古代墓葬》的研究线索,也体现出作者希望以提出若干重要学术概念为依托,重新思考古代中国墓葬美术发展的内在理路。同时所呈现出的叙述与分析风格及美术史观,相对于传统的中国美术通史叙述方式,则具有更为宽广的学术视野。这些特征都为以后的古代中国墓葬美术史研究,提供了一个可以继续探索的桥梁。

Digital reconstruction of ancient Egyptian tombs

From the pyramids of Giza to the tombs of Thebes at Luxor, the glorious ancient Egyptian history has produced remarkable architecture. Sadly, tourists, numbering nearly four million per year, have taken a heavy toll on many of these ancient structures. Of particular concern are many of tombs located opposite Luxor on the western bank of the Nile. Digital reconstruction of these tombs has the potential of helping to document and preserve these important historical structures. Issues concernng new and unique problems involving the photographing and digital reconstruction of these tombs are addressed. Techniques for removing image distortions, recovering 3-D shapes and correcting for lighting imbalances are discussed. A complete reconstruction of the tomb of Sennediem is shown.

Advances in Noble Metal-Decorated Metal Oxide Nanomaterials for Chemiresistive Gas Sensors:Overview

Highly sensitive gas sensors with remarkably low detection limits are attractive for diverse practical application fields including real-time environmental monitoring,exhaled breath diagnosis,and food freshness analysis.Among various chemiresistive sensing materials,noble metal-decorated semiconducting metal oxides(SMOs)have currently aroused extensive attention by virtue of the unique electronic and catalytic properties of noble metals.This review highlights the research progress on the designs and applications of different noble metal-decorated SMOs with diverse nanostructures(e.g.,nanoparticles,nanowires,nanorods,nanosheets,nanoflowers,and microspheres)for high-performance gas sensors with higher response,faster response/recovery speed,lower operating temperature,and ultra-low detection limits.The key topics include Pt,Pd,Au,other noble metals(e.g.,Ag,Ru,and Rh.),and bimetals-decorated SMOs containing ZnO,SnO_(2),WO_(3),other SMOs(e.g.,In_(2)O_(3),Fe_(2)O_(3),and CuO),and heterostructured SMOs.In addition to conventional devices,the innovative applications like photo-assisted room temperature gas sensors and mechanically flexible smart wearable devices are also discussed.Moreover,the relevant mechanisms for the sensing performance improvement caused by noble metal decoration,including the electronic sensitization effect and the chemical sensitization effect,have also been summarized in detail.Finally,major challenges and future perspectives towards noble metal-decorated SMOs-based chemiresistive gas sensors are proposed.

Distribution of Carbon and Oxygen Isotopes in theSequence Stratigraphic Framework of the Middle andUpper Proterozoic in the Ming Tombs Area, Beijing

Abstract: This paper discusses the distribution pattern and geological significance of the carbon and oxygen isotopes (δ13C and δ18O) in the depositional sequences of Gaoyuzhuangian, Yangzhuangian and Wumishanian ages of the established Middle and Upper Proterozoic sequence stratigraphic framework in the Ming Tombs area lying in western Yanshan Mountain of Beijing. Besides, sketchy determination of δ13C and δ18O was also performed for other formations and members. The analytical results show the following: under the condition of clear-water carbonate sediments, δ13C and δ18O, featuring smaller variation of δ13C but larger variation of δ18O, can well delineate the relative change of sea level, which reflects the difference of primary sedimentary settings; in the presence of terrigenous substances, δ13C values vary greatly while δ18O slightly; the carbon and oxygen isotopes show marked changes at sequence boundaries. Besides, particular patterns can be found in regard to the distribution of carbon and oxygen isotopes within the sequences.

Collection of Foreign-made Clocks and Watches Owned By Qing Imperial Nobles

Foreign-made clocks and watches began to be exported to China in the 17th century. During the Qing Dynasty (1644-1911), the imperial court imported tens of thousands of clocks and watches. At the Palace Museum in Beijing, about 200 timepieces collected by the imperial court are still on display in the clock and watch exhibition hall. They were made in Britain, France, Switzerland and Japan. Many foreign presidents and

Towards the selectivity distinction of phenol hydrogenation on noble metal catalysts

Selective hydrogenation of phenol to cyclohexanone is intriguing in chemical industry.Though a few catalysts with promising performances have been developed in recent years,the basic principle for catalyst design is still missing owing to the unclear catalytic mechanism.This work tries to unravel the mechanism of phenol hydro-genation and the reasons causing the selectivity discrepancy on noble metal catalysts under mild conditions.Results show that different reaction pathways always firstly converge to the formation of cyclohexanone under mild conditions.The selectivity discrepancy mainly depends on the activity for cyclohexanone sequential hy-drogenation,in which two factors are found to be responsible,i.e.the hydrogenation energy barrier and the competitive chemisorption between phenol and cyclohexanone,if the specific co-catalyzing effect of H 2 O on Ru is not considered.Based on the above results,a quantitative descriptor,E b(one/pl)/E a,in which E a can be further correlated to the d band center of the noble metal catalyst,is proposed by the first time to roughly evaluate and predict the selectivity to cyclohexanone for catalyst screening.

Finned Zn-MFI zeolite encapsulated noble metal nanoparticle catalysts for the oxidative dehydrogenation of propane with carbon dioxide

Oxidative dehydrogenation of propane with carbon dioxide(CO_(2)-ODP)characterizes the tandem dehydrogenation of propane to propylene with the reduction of the greenhouse gas of CO_(2)to valuable CO.However,the existing catalyst is limited due to the poor activity and stability,which hinders its industrialization.Herein,we design the finned Zn-MFI zeolite encapsulated noble metal nanoparticles(NPs)as bifunctional catalysts(NPs@Zn-MFI)for CO_(2)-ODP.Characterization results reveal that the Zn2+species are coordinated with the MFI zeolite matrix as isolated cations and the NPs of Pt,Rh,or Rh Pt are highly dispersed in the zeolite crystals.The isolated Zn2+cations are very effective for activating the propane and the small NPs are favorable for activating the CO_(2),which synergistically promote the selective transformation of propane and CO_(2)to propylene and CO.As a result,the optimal 0.25%Rh0.50%Pt@Zn-MFI catalyst shows the best propylene yield,satisfactory CO_(2)conversion,and long-term stability.Moreover,considering the tunable synergetic effects between the isolated cations and NPs,the developed approach offers a general guideline to design more efficient CO_(2)-ODP catalysts,which is validated by the improved performance of the bifunctional catalysts via simply substituting Sn4+cations for Zn2+cations in the MFI zeolite matrix.

Imperial Tombs of the Ming and Qing Dynasties

Built between 1368 and 1911, The Imperial Tombs of the Ming （1368- 1644） and Qing （1644-1911） dynaslies includes Xianling Tombs of theMing Dynast）. Eastern and Western Qing Tornbs, Xiaoling Tomb of the Ming Dynasty.

共价有机框架负载贵金属铂用于电催化析氢

我们探究了共价有机框架负载贵金属Pt的电催化析氢性能.以2,6-二氨基蒽醌和2,4,6-三甲酰基间苯三酚为构筑单元,采用溶剂热法合成了TP-DAAQ COF.随后通过金属前驱体浸渍法制备了Pt-TP-DAAQ COF.X射线粉末衍射,傅里叶红外光谱,氮气吸附/脱附等表明成功制备了TP-DAAQ COF和Pt-TP-DAAQ COF.电化学测试结果表明Pt-TP-DAAQ COF(其中含有5.8%的Pt)展现了比20%Pt/C优异的电催化活性.当电流密度为10 mA∙cm^(-2)时,Pt-TP-DAAQ COF的过电位为45 mV,Tafel斜率为29 mV∙dec^(‒1).这高效的电催化活性源于TP-DAAQ COF与Pt之间良好的协同效应.Pt-TP-DAAQ COF具有较大的比表面积和规整的一维孔道,使催化位点更易于与电解液中的物质发生接触和相互作用,从而增强了其催化性能.

松辽盆地天然气中稀有气体地球化学特征及其地质意义

稀有气体地球化学已运用于地球深部物质及天体陨石研究,随着测量技术的进步,在天然气研究中也开始得到越来越多的应用。使用目前最先进的稀有气体质谱仪,对中国东部松辽盆地中深部天然气的稀有气体全组分丰度及同位素进行了系统的分析,明确了断陷盆地稀有气体的组成特征。研究表明,天然气中稀有气体的丰度从轻稀有气体到重稀有气体具有逐渐减小的反“厂”字形趋势。稀有气体的同位素比值^(3)He/^(4)He为2.64×10^(-6)、^(20)Ne/^(22)Ne为9.94、21Ne/^(22)Ne为0.02922、^(40)Ar/^(36)Ar为743.7,均高于大气值,^(80)Kr、^(84)Kr、^(86)Kr、^(131-136)Xe均表现出相对大气过剩的特征,显示天然气中有幔源气体的混入。综合稀有气体的组成特征,说明松辽盆地中深部天然气均为壳幔混源的无机成因,而且不同构造区块、不同类别天然气的幔源组分贡献存在一定差异。对比稀有气体组成与天然气类型发现,轻稀有气体可以较好地区分天然气的类型,而重稀有气体的组成在各种天然气中没有明显差别。稀有气体同位素除了可以示踪天然气来源外,还可以应用在判别天然气成因、区分天然气类型、表征大地构造等方面。

青海都兰热水墓群血渭一号墓2021~2022年清理简报

为了厘清血渭一号大墓的形制与营建,帮助推进文化遗产保护与旅游开发,2021~2022年,热水联合考古队对血渭一号大墓进行了重新清理,清理范围主要包括血渭一号大墓的墓室、附属建筑及大墓南侧的第4、5号殉马沟。通过清理发现,血渭一号墓营建于自然山体平台上,有覆斗式封土,墓室为木石结构的多室墓,附属建筑位于平台东北部,由3座建筑基址组成。血渭一号墓南侧4号殉马沟内发现马骨17具,5号殉马沟内发现马骨21具,结合早年刊布的1~3号殉马沟的马匹数量,可知殉马沟内殉马总数为90具。

牛马不同槽——嘉峪关魏晋墓两幅壁画的现实表达与文化意涵

嘉峪关魏晋墓葬壁画描绘了“牛马不同槽”的现象。结合礼仪艺术与世俗绘卷中的同类图像,揭示了此类现象的现实原因,并指出其进入文化层面后的意涵。先秦哲学从牛马习性出发,抽象出了其间的对立统一关系,很多情境中牛马间的对立还可转化为对应,例如祭祀中的牛马,图像中的牛马合犋犁耕、牧马牧牛、牛车鞍马,宗教语境下的牛头马面等。“牛马不同槽”从民间俗语到文献与图像的表达,反映了古代艺术与生活的密切关系。

湖北云梦县郑家湖墓地M274葬具木材研究

云梦郑家湖C区墓葬均为战国晚期至西汉初的秦文化中小型饱水墓葬。其中M274一棺一椁制且规模较小,从形制规模和随葬品来看,墓主人应当为一名下层吏士。本文作者从M274的棺、椁上分别取样9份,除去一份腐烂严重无法鉴定,其余8份鉴定结果均为紫葳科梓属(Catalpa sp.)。综合文献记载和考古发现,我们认为春秋战国时期,人们已经开始应用梓木,且梓木是楚地乡土树种,就地取材作为棺椁很合理,但当时梓木葬具还不是高等贵族的专属。西汉及以后,梓木葬具与社会等级之间的关系得到强调。

《论语》“君子儒”与“小人儒”涵义考辨

儒家经典《论语》言“儒”,仅见于“女为君子儒,无为小人儒”一章,这很不寻常。学界诠释大多直陈观点而少有理据。要明确“君子儒”“小人儒”词义内涵,考察时代背景尤为重要。分析孔子时代“儒”之卑下地位和柔懦性格,诉诸孔子个人身世抱负及对“新君子”理想人格的塑造,我们认为孔子时代之“儒”都是“小人儒”,即地位低下之儒,“女为君子儒”不过是孔子的期待与自励,希望儒者通过“修德取位”和“以德正位”,成为德位兼具、勇毅刚强的“君子儒”。经孔、孟、荀、董仲舒等历代儒者不断诠释,“君子儒”最终成为两千年来推进政治治理、推动文化发展的中坚。