Monodisperse nickel nanoparticles supported on SiO<Subscript>2</Subscript> as an effective catalyst for the hydrolysis of ammonia-borane

Monodisperse Ni nanoparticles (NPs) have been synthesized by the reduction of nickel(II) acetylacetonate with the borane-tributylamine complex in a mixture of oleylamine and oleic acid. These Ni NPs are an active catalyst for the hydrolysis of the ammonia-borane (AB, H₃N·BH₃) complex under ambient conditions and their activities are dependent on the chemical nature of the oxide support that they were deposited on. Among various oxides (SiO₂, Al₂O₃, and CeO₂) tested, SiO₂ was found to enhance Ni NP catalytic activity due to the etching of the 3.2 nm Ni NPs giving Ni(II) ions and the subsequent reduction of Ni(II) that led to the formation of 1.6 nm Ni NPs on the SiO₂ surface. The kinetics of the hydrolysis of AB catalyzed by Ni/SiO₂ was shown to be dependent on catalyst and substrate concentration as well as temperature. The Ni/SiO₂ catalyst has a turnover frequency (TOF) of 13.2 mol H₂·(mol Ni)⁻¹ · min⁻¹—the best ever reported for the hydrolysis of AB using a nickel catalyst, an activation energy of 34 kJ/mol ± 2 kJ/mol and a total turnover number of 15,400 in the hydrolysis of AB. It is a promising candidate to replace noble metals for catalyzing AB hydrolysis and for hydrogen generation under ambient conditions.     

RuFe纳米粒子修饰片状BiVO4协同催化氨硼烷水解产氢

开发高效廉价的催化剂对于清洁能源经济至关重要, 将氨硼烷的催化水解用于氢能源开发前景广阔。本工作首先采用简单回流法制备BiVO₄纳米片, 再通过浸渍还原法制备出Ru/Fe不同摩尔比的RuFe@BiVO₄催化剂, 并在室温下用于催化氨硼烷水解产氢。通过比较载体BiVO₄、Ru@BiVO₄、Fe@BiVO₄、RuFe@BiVO₄以及无载体的RuFe纳米粒子的催化产氢速率发现, 在所有的催化剂中, Ru₁Fe_0.1@BiVO₄具有最高的催化活性, 非贵金属Fe能显著增强Ru的催化性能, 这与RuFe之间强的电子效应以及RuFe纳米粒子与载体BiVO₄间的双功能效应密切相关, 其活化能(E_a)为43.7 kJ·mol^-1, 转化频率(TOF)为205.4 mol_H2·mol_Ru·min^-1。     

Ru-B催化剂催化NaBH4水解制氢研究

利用化学浸渍-还原法制备出了Ru-B催化剂,考察了催化剂的制备条件和反应条件对Ru-B催化剂催化NaBH4水解制氢性能的影响。结果表明:当活性组分前体RuCl3·6H2O和还原剂NaBH4的物质的量比为1∶7,还原温度为303K时,制得的Ru-B催化剂催化NaBH4水解制氢性能最佳。当催化剂浓度为0.17g/L,反应温度为303K,NaBH4浓度为0.22mol/L,NaOH浓度为0.01mol/L,转速为540r/min时,Ru-B催化剂催化NaBH4水解产氢的速率可达1740mL H2/(min·g)。还发现Ru-B催化剂催化NaBH4水解产氢的速率与催化剂用量呈线性关系,计算得到Ru-B催化剂催化NaBH4水解产氢反应的活化能为23.58kJ/mol。     

Microwave-assisted facile synthesis of palladium nanoparticles in HEPES solution and their size-dependent catalytic activities to Suzuki reaction

Palladium nanoparticles (NPs) were successfully synthesized via a rapid and facile microwave route in HEPES (2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid) buffer solution. The shape- and size-controlled Pd nanoparticles could be obtained by one-step method without dependence of seed-mediated growth. The capping agent plays a key role in the formation of Pd NPs with different shape and size, which could be tuned by varying capping agents such as polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB), sodium citrate (Na3(cit)) and potassium bromide (KBr). The size-dependent catalytic activities of the obtained Pd NPs for Suzuki coupling reaction were also investigated. It demonstrated that the catalytic activity of Pd NPs was enhanced regularly with the decrease of particle size. Pd NPs less than 10 nm exhibited better catalytic activities for Suzuki reaction than the commercial Pd/C catalyst. Pd/MWCNTs and Pd/SBA-15 nanocomposites were also prepared by a facile method and afforded good catalytic activity and reusability. This "green" synthetic protocol could be used as a general method for the rapid synthesis of transition metal nanoparticles.     

Highly Active Metastable Ruthenium Nanoparticles for Hydrogen Production through the Catalytic Hydrolysis of Ammonia Borane

Late transition metal nanoparticles (NPs) with a favorably high surface area to volume ratio have garnered much interest for catalytic applications. Yet, these NPs are prone to aggregation in solution, which has been mitigated through attachment of surface ligands, additives or supports; unfortunately, protective ligands can severely reduce the effective surface area on the NPs available for catalyzing chemical transformations. The preparation of ‘metastable’ NPs can readily address these challenges. We report herein the first synthesis of monodisperse metastable ruthenium nanoparticles (RuNPs), having sub 5 nm size and an fcc structure, in aqueous media at room temperature, which can be stored for a period of at least 8 months. The RuNPs can subsequently be used for the catalytic, quantitative hydrolysis of ammonia‐borane (AB) yielding hydrogen gas with 21.8 turnovers per min at 25 °C. The high surface area available for hydrolysis of AB on the metastable RuNPs translated to an E_a of 27.5 kJ mol^‐1, which is notably lower than previously reported values for RuNP based catalysts.     

SnNi nanoneedles assembled 3D radial nanostructure loaded with SnNiPt nanoparticles: Towards enhanced electrocatalysis performance for methanol oxidation

A desirable methanol oxidation electrocatalyst was fabricated by metal atom diffusion to form an alloy of an assembled three-dimensional (3D) radial nanostructure of SnNi nanoneedles loaded with SnNiPt nanoparticles (NPs).Herein,metal atom diffusion occurred between the SnNi support and loaded Pt NPs to form a SnNiPt ternary alloy on the catalyst surface.The as-obtained catalyst combines the excellent catalytic performance of the alloy and advantages of the 3D nanostructure;the SnNiPt NPs,which fused on the surface of the SnNi nanoneedle support,can dramatically improve the availability of Pt during electrocatalysis,and thus elevate the catalytic activity.In addition,the efficient mass transfer of the 3D nanostructure reduced the onset potential.Furthermore,the catalyst achieved a favorable CO poisoning resistance and enhanced stability.After atomic interdiffusion,the catalytic activity drastically increased by 45％,and the other performances substantially improved.These results demonstrate the significant advantage and enormous potential of the atomic interdiffusion treatment in catalytic applications.     

Synthesis and characterization of PtRe alloy nanoparticles as electrocatalysts for methanol oxidation

We report a new synthesis of PtRe alloy nanoparticles (NPs) and their electrocatalytic activity for methanol oxidation. PtRe alloy NPs with controlled composition were prepared by a capping agents-based colloidal method. In the synthesis, trioctylamine was used as high-boiling solvent, and oleylamine/oleic acid were employed as capping agents to control the particle size and dispersion. The PtRe NPs were fully characterized by TEM, EDX, XRD and XPS. The as-prepared PtRe NPs had a narrow size distribution, and displayed a good dispersion in hydrocarbon solvents. Carbon-supported PtRe catalysts were prepared by physical deposition of as-prepared particles on carbon powder, followed by the catalytic activation at 400 degrees C in Ar/H2. Electrochemical studies showed the PtRe catalysts had high activity for methanol electrooxidation.     

A General Strategy Assisted with Dual Reductants and Dual Protecting Agents for Preparing Pt‐Based Alloys with High‐Index Facets and Excellent Electrocatalytic Performance

Synthesizing noble metallic nanoparticles (NPs) enclosed by high‐index facets (HIFs) is challenged as it involves the tuning of growth kinetics, the selective adsorption of certain chemical species, and the epitaxial growth from HIF enclosed seeds. Herein, a simple and general strategy is reported by using dual reduction agents and dual capping agents to prepare Pt‐based alloy NPs with HIFs, in which both glycine and poly(vinylpyrrolidone) serve as the reductants and capping agents. Due to the facilely tunable growth/nucleation rates and protecting abilities of the reductants and capping agents, Pt concave nanocube (CNC), binary Pt–Ni CNC, ternary Pt–Mn–Cu CNC, and Pt–Mn–Cu ramiform polyhedron alloy NPs terminated by HIFs as well as other NPs with well‐defined morphologies such as Pt–Mn–Cu nanocube and Pt–Mn–Cu nanoflower are obtained with this approach. Owing to the high density of low‐coordinated Pt sites (HIF structure) and the unique electronic effect of Pt–Mn–Cu ternary alloys, the as‐prepared Pt–Mn–Cu NPs show enhanced catalytic activity toward methanol and formic acid electro‐oxidation reactions with excellent stability. This work provides a promising methodology for designing and fabricating Pt‐based alloy NPs as efficient fuel cell catalyst.     

Hydrogen Storage Alloy and Carbon Nanotubes Mixed Catalyst in a Direct Borohydride Fuel Cell

In this study, carbon nanotubes (CNTs) were mixed with AB5-type hydrogen storage alloy (HSA), as catalyst for an anode in a direct borohydride fuel cell (DBFC). As comparision, a series of traditional carbon materials, such as acetylene black, Vulcan XC-72R, and super activated carbon (SAC) were also employed. Electrochemical measurements showed that the electrocatalytic activity of HSA was improved greatly by CNTs. The current density of the DBFC employing the HSA/CNTs catalytic anode could reach 1550 mA·cm-2 (at -0.6 V vs the Hg/HgO electrode) and the maximum power density of 65 mW·cm-2 for this cell could be achieved at room temperature. Furthermore, the life time test lasting for 60 h showed that the cell displayed a good stability.     

具有三维网状结构的石墨相氮化碳/还原氧化石墨烯/钯复合材料的合成及可见光催化性能

石墨相氮化碳(g-C_3N_4)已经被认为是一种高效的非金属半导体光催化剂。为进一步优化其光催化性能,通过热解-水热两步法制备了三维网状结构的g-C_3N_4/还原氧化石墨烯(rGO)/钯纳米颗粒(Pd NPs)复合材料。该复合材料由大量超薄片组成,而且薄片上有大量直径约为10nm的Pd NPs。g-C_3N_4/rGO/Pd NPs复合材料展现了一个宽的可见光吸收(边~460nm),其在460~800nm波长范围内还有一个随波长增加的光吸收。经可见光(λ400nm)照射140 min后,g-C_3N_4/rGO/Pd NPs复合材料可降解90%罗丹明B(RhB)。此外,循环实验表明g-C_3N_4/rGO/Pd NPs复合材料具有良好的稳定性。因此,g-C_3N_4/rGO/Pd NPs复合材料有望成为一种高效稳定的光催化剂,在水污染处理领域具有潜在的应用价值。     

Ternary Pd–Ni–P nanoparticle-based nonenzymatic glucose sensor with greatly enhanced sensitivity achieved through active-site engineering

We develop a unique ternary Pd-Ni-P nanocatalyst for the sensitive enzymefree electrooxidation detection of glucose under alkaline conditions.By reducing the distance between the Pd and Ni active sites in the Pd-Ni-P nanoparticles (NPs) via atom engineering,the catalyst structure is transformed from Pd@Ni-P dumbbells into spherical NPs,greatly enhancing the catalyst sensitivity.The glassy carbon electrode modified with Pd-Ni-P ternary NPs,which behaves as an efficient nonenzymatic glucose sensor,offers excellent electrocatalytic performance with a high sensitivity of 1,136 μA·mM-1·cm-2,a short response time of 2 s,a wide linear range of 0.5 ~ to 10.24 mM,a low limit of detection of 0.15 μM (signal-to-noise ratio =3),and good selectivity and reproducibility.Moreover,owing to its superior catalytic performance,the Pd-Ni-P modified electrode has excellent reliability for glucose detection in real samples of human serum.Our study provides a promising alternative strategy for designing and constructing high-performance multicomponent nanocatalyst-based sensors.     

Co3O4电化学电容电极材料的制备及性能研究

利用水热法,以硝酸钴为原料,分别以碳酸氢铵、六次甲基四胺为沉淀剂,制备了Co3O4。借助X射线衍射、扫描电子显微镜手段对样品进行表征。以六次甲基四胺为沉淀剂制得的Co3O4,在6 mol.L-1KOH水溶液中,电位窗口为0～0.4V内,通过循环伏安和恒流充放电测试,显示该材料制备的电极具有良好的电容行为。充放电流在为5 mA时,单电极的比容量达到239 F.g-1,是以碳酸氢铵为沉淀剂制得的Co3O4电极的1.57倍,说明以六次甲基四胺为沉淀剂制备的Co3O4具有较好的电化学电容性能。     

Co@Co3O4@PPD Core@bishell Nanoparticle‐Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high‐performance primary zinc‐air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co₃O₄ core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co₃O₄@PPD core@bishell structure, obtained via a three‐step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co₃O₄ NPs encapsulated by ultrathin highly graphitized N‐doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N‐doped graphitic carbon outer shell and ultrathin nanocrystalline Co₃O₄ inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co₃O₄@PPD in air‐cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm^?2.     

Catalytic Hydrogenation of CO2 to Formate Using Ruthenium Nanoparticles Immobilized on Supported Ionic Liquid Phases

Ruthenium nanoparticles (NPs) immobilized on imidazolium-based supported ionic liquid phases (Ru@SILP) act as effective heterogeneous catalysts for the hydrogenation of carbon dioxide (CO₂) to formate in a mixture of water and triethylamine (NEt₃). The structure of the imidazolium-based molecular modifiers is varied systematically regarding side chain functionality (neutral, basic, and acidic) and anion to assess the influence of the IL-type environment on the NPs synthesis and catalytic properties. The resulting Ru@SILP materials contain well-dispersed Ru NPs with diameters in the range 0.8–2.9 nm that are found 2 to 10 times more active for CO₂ hydrogenation than a reference Ru@SiO₂ catalyst under identical conditions. Introduction of sulfonic acid groups in the IL modifiers results in a greatly increased turnover number (TON) and turnover frequency (TOF) at reduced metal loadings. As a result, excellent productivity with TONs up to 16 100 at an initial TOF of 1430 h⁻¹ can be achieved with the Ru@SILP(SO₃H-OAc) catalyst. H/D exchange and other control experiments suggest an accelerated desorption of the formate species from the Ru NPs promoted by the presence of ammonium sulfonate species on Ru@SILP(SO₃H-X) materials, resulting in enhanced catalyst activity and productivity.     

Hydrolytic dehydrogenation of ammonia borane catalyzed by poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets supported Ag0.3Co0.7 nanoparticles

Poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets (PAMAM/rGO) composite was selected as a carrier of heterogeneous Ag_0.3Co_0.7 nanoparticles in order to obtain an excellent catalyst for ammonia borane (AB) hydrolysis. During the synthetic processes, GO could easily assembled with PAMAM by the electrostatic and hydrogen-bonding interactions. Structural characterization revealed that Ag_0.3Co_0.7 bimetallic nanoparticles with uniform size distribution of 5 nm are well dispersed on PAMAM/rGO composite architecture. Ag_0.3Co_0.7@PAMAM/rGO was found to be a highly active and reusable catalyst in hydrogen generation from the hydrolysis of AB with a turnover frequency value (TOF) of 19.79 mol_H2 min^–1 mol_M^–1 at 25.0 ± 0.1 °C and retained 75.4% of their initial activity with a complete release of hydrogen in five runs. The relatively high TOF value and low apparent activation energy (34.21 kJ mol^–1) make these Ag_0.3Co_0.7@PAMAM/rGO NPs as a high-efficient catalyst for catalytic dehydrogenation of AB facilitating the development of practically applicable energy storage materials.     

Stable single-crystalline body centered cubic Fe nanoparticles

We report a facile synthesis of body centered cubic (bcc) Fe nanoparticles (NPs) via the thermal decomposition of iron pentacarbonyl, Fe(CO)(5), in the presence of hexadecylammonium chloride. These bcc-Fe NPs exhibit a drastically increased stability and magnetic moment (M(s) = 164 A·m(2)·kg(-1)(Fe)) even in physiological solutions, and have much enhanced magnetic imaging contrast (r(2) = 220 s(-1)·mM(-1)) and heating (SAR = 140 W·g(-1)(Fe)) effects. They may serve as robust probes for imaging and therapeutic applications.     

空心结构(C12H8N2)3·H3PMo12O40/WO3的制备及光催化研究

制备了杂多化合物(C12H8N2)3.H3PMo12O40和空心结构复合催化剂(C12H8N2)3.H3PMo12O40/WO3,采用等离子体原子发射光谱(ICP-AES)、元素分析(EA)、热重-差热分析(TG-DTA)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电镜(SEM)、能量色散X射线谱(EDS)、紫外-可见漫反射吸收光谱(UV-vis DRS)进行了表征。在高压汞灯照射下,研究了杂多化合物(C12H8N2)3.H3PMo12O40、空心WO3微球和空心复合催化剂(C12-H8N2)3.H3PMo12O40/WO3对罗丹明B水溶液的光催化降解活性,结果表明,在复合催化剂中,杂多化合物(C12-H8N2)3.H3PMo12O40和WO3具有协同作用,光催化活性比单独的杂多化合物和WO3都高。     

All electrochemical fabrication of a platinized nanoporous Au thin-film catalyst

In an effort to decrease the high cost associated with the design, testing, and production of electrocatalysts, a completely electrochemical scheme has been developed to deposit and platinize a nanoporous Au (NPG) based catalyst for formic acid oxidation. The proposed route enables synthesis of an alternative to the most established, nanoparticles based catalysts and addresses issues of the latter associated with either contamination inherent from the synthetic route or poor adhesion to the supporting electrode. The synthetic protocol includes as a first step, electrochemical codeposition of a Au((1-x))Ag(x) alloy in a thiosulfate based electrolyte followed by selective electrochemical dissolution (dealloying) of Ag as the less noble metal, that generates an ultrathin and preferably continuous porous structure featuring thickness of less than 20 nm. NPG is then functionalized with Pt (no thicker than 1 nm) by surface limited redox replacement (SLRR) of underpotentially deposited Pb layer to form Pt-NPG. SLRR ensures complete coverage of the surface with Pt, believed to spread evenly over the NPG matrix. Testing of the catalyst at a proof-of-concept level demonstrates its high catalytic activity toward formic acid oxidation. Current densities of 40-50 mA cm(-2) and mass activities of 1-3 A.mg(-1) (of combined Pt-Au catalyst) have been observed and the Pt-NPG thin films have lasted over 2600 cycles in standard formic acid oxidation testing.     

氯盐环境中新型合金耐蚀钢筋Cr10Mo1的钝化行为

应用线性极化、电化学阻抗谱与电容电位法等方法对比研究了合金耐蚀钢筋Cr10Mo1和普通碳素钢筋在预含不同浓度(0mol·L~(-1)、0.1mol·L~(-1)、0.3mol·L~(-1)、0.6mol·L~(-1))氯盐的较低碱度(pH=12.5)模拟混凝土孔溶液中的钝化行为,利用XPS方法分析钢筋钝化膜组成结构,分析了氯盐作用下两种钢筋钝化行为变化存在差异的原因,揭示了合金耐蚀钢筋强易钝化机制。结果表明:在各氯盐浓度下,合金耐蚀钢筋均能良好致钝且钝化效果并无较大差距,而普通碳素钢筋随氯盐浓度增大钝化效果显著减弱,当氯盐超过一定浓度则几乎不钝化,甚至发生明显点蚀。Cr氧化物作为合金耐蚀钢筋钝化膜不同于普通碳素钢筋的关键成分,高浓度氯盐作用下仍可保持稳定并维持钝化膜层完整密实,从而使耐蚀钢筋呈现强易致钝特性。     

Highly Efficient Photoelectrocatalytic Reduction of CO2 to Methanol by a p–n Heterojunction CeO2/CuO/Cu Catalyst

Photoelectrocatalytic reduction of CO2 to fuels has great potential for reducing anthropogenic CO2 emissions and also lessening our dependence on fossil fuel energy.Herein,we report the successful development of a novel photoelectrocatalytic catalyst for the selective reduction of CO2 to methanol,comprising a copper catalyst modified with flower-like cerium oxide nanoparticles(CeO2 NPs)(a n-type semiconductor)and copper oxide nanoparticles(CuO NPs)(a p-type semiconductor).At an applied potential of−1.0 V(vs SCE)under visible light irradiation,the CeO2 NPs/CuO NPs/Cu catalyst yielded methanol at a rate of 3.44μmol cm^−2 h^−1,which was approximately five times higher than that of a CuO NPs/Cu catalyst(0.67μmol cm^−2 h^−1).The carrier concentration increased by^108 times when the flower-like CeO2 NPs were deposited on the CuO NPs/Cu catalyst,due to synergistic transfer of photoexcited electrons from the conduction band of CuO to that of CeO2,which enhanced both photocatalytic and photoelectrocatalytic CO2 reduction on the CeO2 NPs.The facile migration of photoexcited electrons and holes across the p–n heterojunction that formed between the CeO2 and CuO components was thus critical to excellent light-induced CO2 reduction properties of the CeO2 NPs/CuO NPs/Cu catalyst.Results encourage the wider application of composite semiconductor electrodes in carbon dioxide reduction.