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-C_(3)N_(4) 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.

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.

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.

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.

Catalytic removal of volatile organic compounds using ordered porous transition metal oxide and supported noble metal catalysts

Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.

基于局部熵和方差调整的Noble角点检测算法改进

为了提高角点检测精度,增强算法对伪角点的抑制能力,在Noble算子的基础上充分考虑图像不同区域间灰度统计特性的差异,提出了一种基于局部熵和方差调整的Noble角点检测改进算法.该算法首先选择角点响应函数阈值以及非极大值抑制邻域大小的初始参考值,然后根据区域熵与区域方差分别估计这两个初始参考值的局部调整系数,最后用调整系数对随后的参考值进行加权,获得自适应于真实信号结构的局部阈值以及局部非极大值抑制邻域大小.实验结果表明,所提算法能够精确地检测出大部分真实角点,有效地消除伪角点的干扰.

孤立心肌桥病人静息心率、左心室结构和收缩功能与Noble分级的关系

目的探讨孤立心肌桥病人静息心率、左心室结构和收缩功能与Noble分级的关系。方法选取2015年—2017年内蒙古自治区巴彦淖尔市医院心内科住院的孤立心肌桥病人111例,按照静息心率水平分为3组,A组41例(静息心率<70次/min)、B组48例(静息心率70~<80次/min)、C组22例(静息心率≥80次/min)。分析影响孤立心肌桥病人心率及Noble分级的因素。结果静息心率与心肌桥Noble分级呈正相关(r=0.612,P=0.000)。左心室射血分数(LVEF)、室间隔厚度(IVST)对静息心率有影响;LVEF、左心室质量(LVM)、左心室质量指数(LVMI)对Noble分级有影响(均P<0.05)。结论孤立心肌桥病人静息心率与心肌桥Noble分级呈正相关,可通过不同水平静息心率与LVEF、LVM、LVMI评估心肌桥Noble分级情况。

Noble型分块态射的Moore-Penrose逆

讨论了加法范畴中Noble型分块态射m=[acbd]的Moore-Penrose逆,且给出了Moore-Penrose逆的表达式.

Syngas Production by Methane Reforming with Carbon Dioxide on Noble Metal Catalysts

A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.

Efficient Separation of Ar and Kr from Environmental Samples for Trace Radioactive Noble Gas Detection

Radioactive noble-gas isotopes, SSKr （half-life tl/2=10.8 y）, 39Ar （tl/2=269 y）, and SlKr （t1/2-229,000 y）, are ideal tracers and can be detected by atom trap trace analysis （ATTA）, a laser-based technique, from environmental samples like air and groundwater. Prior to ATTA measurements, it is necessary to efficiently extract krypton and argon gases from samples. Using a combination of cryogenic distillation, titanium chemical reaction and gas chromatography, we demonstrate that we can recover both krypton and argon gases from 1-10 L ＂air-like＂ samples with yields in excess of 90% and 98%, respectively, which meet well the requirements for ATTA measurements. A group of testing samples are analyzed to verify the performance of the system, including two groundwater samples obtained from north China plain.

Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He. Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic areathan do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4‰ to 1.6 ‰ and from -52.8‰ to -2.8‰, respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and near-surface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantle-derived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the Tengchong magmatic component. Compared with MORB, this relative low 3He/4He ratio could be fully attributed to either deep crustal contamination, or radioactive aging, or past contamination of the local mantle by U- and Th-rich subducted crustal material. However, a combination of low 3He/4He, high radiogenic 4He/40Ar ratio and identical CO2/3He and δ13Cco2 relative to MORB may suggest addition of prior subductedd crsustal material (ca 1 %-2%) to the MORB reservoir around 1.3 Ga ago, which is essentially compatible with the LIL-elements, and Sr-Nd-Pb isotopes of volcanic rocks.

Surface/interface engineering of high-efficiency noble metal-free electrocatalysts for energy-related electrochemical reactions

To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.

S, C, O, H Isotope Data and Noble Gas Studies of the Maoniuping LREE Deposit, Sichuan Province, China: A Mantle Connection for Mineralization

The Maoniuping REE deposit, located about 22 km to the southwest of Mianning, Sichuan Province, is the second largest light REE deposit in China, subsequent to the Bayan Obo Fe-Nb-REE deposit in the Inner Mongolia Autonomous Region. Tectonically, it is located in the transitional zone between the Panxi rift and the Longmenshan-Jinpingshan orogenic zone. It is a carbonatite vein-type deposit hosted in alkaline complex rocks. The bastnaesite-barite, bastnaesite-calcite, and bastnaesite- microcline lodes are the main three types of REE ore lodes. Among these, the first lode is distributed most extensively and its REE mineralization is the strongest. The δ^34Sv.cDT values of the barites in the ore of the deposit vary in a narrow range of ＋5.0 to ＋5.1‰ in the bastnaesite-calcite lode and ＋3.3 to ＋5.9‰ in the bastnaesite-barite lode, showing the isotopic characteristics of magma-derived sulfur. The δ^13Cv-PDB values and the δ^Ov.SMOW values in the bastnaesite-calcite lode range from -3.9 to -6.9‰ and from ＋7.3 to ＋9.7 ‰, respectively, which fall into the range of ＂primary carbonatltes＂, showing that carbon and oxygen in the ores of the Maoniuping deposit were derived mainly from a deep source. The δ^13Cv.PDB values of fluid inclusions vary from -3.0 to -5.6‰, with -3.0 to -4.0‰ in the bastnaesitecalcite lode and -3.0 to -5.6‰ in the bastnaesite-barite lode, which show characteristics of mantle- derived carbon. The δDv-SMOW values of fluid inclusions range from -57 to -88‰, with -63 to -86‰ in the bastnaesite-calcite lode and -57 to -88‰ in the bastnaesite-barite lode, which show characteristics of mantle-derived hydrogen. The δ^18OH2OV.SMOW values vary from ＋7.4 to ＋8.6‰ in the bastnaesitecalcite lode, and ＋6.7 to ＋7.8‰ in the bastnaesite-barite lode, almost overlapping the range of ＋5.5 to ＋9.5‰ for magmatic water. The 4He content, R/Ra ratios are （13.95 to 119.58）×10^-6 （cm^3/g）STP and 0.02 to 0.11, respectively, and ^40Ar/^36Ar is 313± 1 to 437 ± 2. Considering the 4He increase caused by high contents of radioactive elements, a mantle-derived fluid probably exists in the inclusions in the fluorite, calcite and bastnaesite samples. The Maoniuping deposit and its associated carbonatite-alkaline complex were formed in 40.3 to 12.2 Ma according to K-Ar and U-Pb data. All these data suggest that large quantities of mantle fluids were involved in the metallogenic process of the Maoniuping REE deposit through a fault system.

Geochemical characteristics of noble gases in natural gas and their application in tracing natural gas migration in the middle part of the western Sichuan Depression, China

Noble gases in natural gas, from Xiaoquan, Xinchang, Hexingchang and Fenggu gas reservoirs in the middle part of the western Sichuan Depression, China, were analysed. Results show that the volume content of crustal noble gases accounts for 97.9% to 99.7% of the total noble gas content, indicating that the noble gases in the study area are very largely derived from the crust. Moreover, the 40Ar time-accumulating effect of source rocks is used to determine the complex relationship between gases and source rocks in this area, and the results agree well with that from analysis of source rock light hydrocarbons. Due to the short migration distance, the separation of 4He and 40Ar is not significant in Xujiahe natural gas and Lower and Middle Jurassic natural gas, so it is difficult to trace natural gas migration. However, this separation characteristic of 4He and 40Ar in Middle and Upper Jurassic natural gas is significant, which indicates that natural gas migration was from the Middle Jurassic to Upper Jurassic formations. In addition, the variation trends of 3He/4He ratio and δ13C1 value indicates that natural gas migration is from the Xujiahe formation to the Jurassic layer in the study area.

Light alloying element‐regulated noble metal catalysts for energy‐related applications

Noble metals have been widely used as heterogeneous catalysts because they exhibit high activity and selectivity for many reactions of both academic and industrial interest.The introduction of light atomic species(e.g.,H,B,C,and N)into noble metal lattices plays an important role in optimizing catalytic performance by modulating structural and electronic properties.In this review,we present a general overview of the recent advances in the modification of noble metals with light alloying elements for various catalytic reactions,particularly for energy‐related applications.We summarize the types,location,concentration,and ordering degree of light atoms as major factors in the performance of noble metal‐based catalysts,with emphasis on how they can be rationally controlled to promote activity and selectivity.We then summarize the synthetic strategies developed to incorporate light elements and highlight the theoretical and experimental methods for understanding the alloying effects.We further focus on the wide usage of noble metal‐based catalysts modified with different light alloying atoms and attempt to correlate the structural features with their catalytic performances.Finally,we discuss current challenges and future perspectives regarding the development of highly efficient noble metal‐based catalysts modified with light elements.

Plasmon Assisted Highly Efficient Visible Light Catalytic CO_(2) Reduction Over the Noble Metal Decorated Sr-Incorporated g-C_(3)N_(4)

The photocatalytic performance of g-C_(3)N_(4) for CO_(2) conversion is still inadequate by several shortfalls including the instability,insu cient solar light absorption and rapid charge carrier's recombination rate. To solve these problems,herein,noble metals(Pt and Au)decorated Sr-incorporated g-C_(3)N_(4) photocatalysts are fabricated via the simple calcination and photo-deposition methods. The Sr-incorporation remarkably reduced the g-C_(3)N_(4) band gap from 2.7 to 2.54 eV,as evidenced by the UV–visible absorption spectra and the density functional theory results. The CO_(2) conversion performance of the catalysts was evaluated under visible light irradiation. The Pt/0.15 Sr-CN sample produced 48.55 and 74.54 μmol h-1 g-1 of CH_(4) and CO,respectively.These amounts are far greater than that produced by the Au/0.15 Sr-CN,0.15 Sr-CN,and CN samples. A high quantum e ciency of 2.92% is predicted for the Pt/0.15 Sr-CN sample. Further,the stability of the photocatalyst is confirmed via the photocatalytic recyclable test. The improved CO_(2) conversion performance of the catalyst is accredited to the promoted light absorption and remarkably enhanced charge separation via the Sr-incorporated mid gap states and the localized surface plasmon resonance e ect induced by noble metal nanoparticles.This work will provide a new approach for promoting the catalytic e ciency of g-C_(3)N_(4) for e cient solar fuel production.

Calculation of phonon spectrum for noble metals by modified analytic embedded atom method （MAEAM）

In the harmonic approximation, the atomic force constants are derived and the phonon dispersion curves along four major symmetry directions [00ζ], [0ζζ], [ζζζ] and [0ζ1] （or △∑, A and Z in group-theory notation） are calculated for four noble metals Cu, Ag, Au and Pt by combining the modified analytic embedded atom method （MAEAM） with the theory of lattice dynamics. A good agreement between calculations and measurements, especially for lower frequencies, shows that the MAEAM provides a reasonable description of lattice dynamics in noble metals.