In situ synthesis of metallophthalocyanines into pores of MIL‐101: A novel and green strategy for preparation of host–guest catalysts

A novel strategy is developed to encapsulate metallophthalocyanines (MPcs, M = Cu, Ni and Co) into MIL‐101 to give MPcs@MIL‐101 via in situ synthesis of MPcs from component fragments in 1‐butyl‐3‐methylimidazolium bromide as an ionic liquid. This strategy overcomes some drawbacks of existing methods for encapsulation of MPcs into metal–organic frameworks. The chemical and structural properties of MPcs@MIL‐101 were determined using scanning electron microscopy, powder X‐ray diffraction, and Fourier transformation infrared and flame atomic absorption spectroscopies. The results showed that CuPc@MIL‐101, which was used as a ‘ship‐in‐a‐bottle’ catalyst, demonstrates excellent catalytic performance in the oxidative amidation of aldehydes with amine salts. It is confirmed that CuPc@MIL‐101 can be reused up to five times without significant loss of its activity.     

Thiochalcone substituted phthalocyanines for dye-sensitized solar cells: Relation of optical and electrochemical properties for cell performance

The new peripherally tetra-substituted metallophthalocyanines (MPcs, M=Zn, Co, Ni) bearing the chalcone, (E)-3-(4-hydroxyphenyl)-1-(thiophen-2-yl)prop-2-en-1-one, for dye-sensitized solar cells (DSSCs) were synthesized. FT-IR, ¹H NMR, ¹³C NMR, and UV–Vis spectroscopy techniques were utilized for characterization of all the MPcs. Electrochemical, optical and photovoltaic properties of all the MPcs as sensitizers were examined. Electrochemical studies reveal that while the ZnPc (4) and NiPc (6) give only Pc ring-based redox reactions, the CoPc (5) shows redox reactions based on both the central metal and the ring due to the metal 3d orbitals lying between the Pc HOMO and LUMO. The DSSC based on 5 gave the lowest power conversion efficiency (0.51%), perhaps due to the presence of a redox active central metal ion in the core of the complex, which results in a decrease electron transfer in the device. However, cells based on the other complexes including redox inactive central metal ions, which cannot reduce electron transfer, showed reasonable power conversion efficiencies of 1.27% and 1.11% for 4 and 6, respectively. The slight difference between the efficiencies can be attributed to higher molar extinction coefficient and narrower band gap of 4 than 6, which ensure a higher photocurrent and broader light absorption in the visible region.     

银离子修饰的介孔磷钨酸/二氧化硅催化剂氧化脱硫性能研究

采用银修饰介孔磷钨酸/二氧化硅（mesoporous HPW/SiO₂）催化剂,并研究了其在模拟柴油和真实柴油氧化脱硫反应中的催化性能。通过银修饰介孔HPW/SiO₂,结合银离子对有机硫化物的选择吸附性和HPW对有机硫化物的催化氧化活性,以达到选择氧化脱硫的目的。模拟柴油分别采用石油醚、苯、1-辛烯和二苯并噻吩配制,当银离子与HPW的摩尔比为2时,催化剂具有最高的选择催化氧化活性。采用N₂ 吸附-脱附、XRD、UV-vis和EDS表征了银修饰的介孔HPW/SiO₂催化剂,结果表明,银物种分散均匀且以Ag⁺形式存在。真实柴油的脱硫研究表明,相比介孔HPW/SiO₂催化剂,修饰的催化剂介孔Ag₂-HPW/SiO₂脱硫率提高了4.6%,初始硫含量为1800×10^-6的直馏柴油能被脱除至228×10^-6,脱硫率为87.3%。介孔Ag₂-HPW/SiO₂催化剂具有良好的再生性能,经再生处理后,Ag的损失量极少,其三次脱硫率达到84.8%。     

Synthesis,structure, magnetism,and electrochemical properties of a linear pentanuclear Ni5 compound derived from an oligo-α-pyridylamino ligand: Ni5(μ-dmpdda)4(NCS)2

The synthesis, crystal structures, electrochemical, and magnetic properties of a linear pentanuclear Ni₅ compound derived from an oligo-α-pyridylamino ligand, [Ni₅(μ-dmpdda)₄(NCS)₂] [dmpdda-H₂ = N,N′-di(4-methylpyridin-2-yl)pyridine-2,6-diamine], are reported. Ni₅(μ-dmpdda)₄(NCS)₂ involve a Ni₅ linear chain unit with all of the Ni–Ni–Ni angles being nearly 180°, terminated by two axial ligands. The pentanuclear linear metal chain is helically wrapped by four syn–syn–syn–syn type dmpdda^2? ligands. There are two types of Ni–Ni distances in this complex. Terminal Ni–Ni distances bonded with the axial ligand are longer (2.377 Å); the inner Ni–Ni distances are short at 2.2968 Å. Terminal Ni(II) ions bonded with the axial ligands are square-pyramidal (NiN₄NCS) with long Ni–N bonds (2.092 Å), consistent with a high-spin Ni(II) configuration. The inner three Ni(II) ions have short Ni–N (1.901–1.925 Å) bond distances, consistent with a square planar (NiN₄), diamagnetic arrangement of a low-spin Ni(II) configuration. This compound exhibits magnetic behavior similar to [Ni₅(μ-tpda)₄(NCS)₂], indicating an antiferromagnetic interaction of two terminal high-spin Ni(II) ions.     

Highly sensitive spectrofluorimetric determination of cysteine by Cu2+-morin complex

p-Toluenesulfonylamide was immobilized on silica gel and on nm-sized silicium dioxide (SiO₂). Their adsorption efficiency toward metal ions was investigated by the batch equilibrium technique. Although silica gel and nm-SiO₂ have the same composition (silicon and oxygen), the difference in their sizes and surface structures results in distinct chemical activity and selectivity. At pH 4, the adsorption capacity of modified silica gel adsorbent was found to be 4.9, 5.0, 33.2, and 12.6 mg g⁻¹ for Cr(III), Cu(II), Pb(II) and Zn(II), respectively. However, the adsorption capacity of nm-SiO₂ adsorbent toward Cr(III) was 26.7 mg g⁻¹ under ultrasonic dispersing. The potential application of p-toluenesulfonylamide-modified silica gel for simultaneous preconcentration of trace chromium, copper, lead and zinc from two standard reference materials and two food samples was performed with satisfactory results. Correspondence: Xijun Chang, Department of Chemistry, Lanzhou University, Lanzhou 730000, P.R. China     

Efficient oxidative degradation of 2-chlorophenol and 4-chlorophenol over supported CuO-based catalysts

A series of metal oxide catalysts for catalytic oxidative degradation of 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP) were prepared, and the supported CuO catalysts were studied particularly. The supported CuO catalysts were characterized by XRD and NH3-TPD techniques, in which CuO/γ-Al2O3 exhibited high degradation activity. The addition of Na2O or K2O into CuO/γ-Al2O3 improved the oxidative degradation of CPs remarkably, in which Na2O was more efficient than K2O. Over CuO/γ-Al2O3-Na2O, CPs were completely converted and the liberation of the inorganic chloride from 2-CP or 4-CP reached 97% or 100% respectively at 30 ?C for 2 h. The supported CuO catalysts with good dispersion of CuO particles and less acid sites were favorable for the efficient oxidative degradation of CPs. In addition, the initial pH of the reaction solution was found to be an important factor which influenced the catalytic oxidative degradation of CPs and the initial pH of 11.2 and 9.8 was preferred for the oxidative degradation of 2-CP and 4-CP respectively over CuO/γ-Al2O3 catalyst.     

AgI/h-MoO3异质结的构筑及其模拟燃油光催化氧化脱硫活性

利用沉积法获得了异质结AgI/h-MoO₃光催化剂,通过X射线衍射（XRD）、扫描电子显微镜（SEM）、光电子能谱（EDS）、X射线光电子能谱（XPS）、紫外-可见漫反射吸收光谱（UV-Vis-DRS）、光致发光（PL）、电化学阻抗（EIS）等方法对其物相组成、形貌、光吸收特性、光电化学性能等进行了表征。以噻吩的正辛烷溶液模拟催化裂化（FCC）汽油为探针考察了AgI/h-MoO₃光催化氧化脱硫活性,结果表明,AgI/h-MoO₃-18异质结在催化剂浓度为1.5 g·L^-1,可见光照射2 h后,光催化氧化脱硫活性达98%。利用XRD、XPS、UV-Vis-DRS揭示了AgI/h-MoO₃光照后生成少量的金属Ag,使其结构转变为Z型AgI/Ag/h-MoO₃,有利于光生电子（e^-）转移。利用活性物种捕获实验、循环实验研究了AgI/h-MoO₃光催化氧化脱硫机理及其稳定性,实验结果表明：AgI/h-MoO₃不仅具有较高的光催化氧化脱硫活性,而且还有良好的稳定性。     

AgI/h-MoO_3异质结的构筑及其模拟燃油光催化氧化脱硫活性

利用沉积法获得了异质结AgI/h-MoO_3光催化剂,通过X射线衍射(XRD)、扫描电子显微镜(SEM)、光电子能谱(EDS)、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis-DRS)、光致发光(PL)、电化学阻抗(EIS)等方法对其物相组成、形貌、光吸收特性、光电化学性能等进行了表征。以噻吩的正辛烷溶液模拟催化裂化(FCC)汽油为探针考察了AgI/h-MoO_3光催化氧化脱硫活性,结果表明,AgI/h-MoO_3-18异质结在催化剂浓度为1.5 g·L~(-1),可见光照射2 h后,光催化氧化脱硫活性达98%。利用XRD、XPS、UV-Vis-DRS揭示了AgI/h-MoO_3光照后生成少量的金属Ag,使其结构转变为Z型AgI/Ag/h-MoO_3,有利于光生电子(e~-)转移。利用活性物种捕获实验、循环实验研究了AgI/h-MoO_3光催化氧化脱硫机理及其稳定性,实验结果表明:AgI/h-MoO_3不仅具有较高的光催化氧化脱硫活性,而且还有良好的稳定性。     

Preparation of morin modified nanometer SiO<Subscript>2</Subscript> as a sorbent for solid-phase extraction of trace heavy metals from biological and natural water samples

Morin was successful as a chemical modifier to improve the reactivity of the nanometer SiO₂ surface in terms of selective binding and extraction of heavy metal ions. This new functionalized nanometer SiO₂ (nanometer SiO₂-morin) was used as an effective sorbent for the solid-phase extraction (SPE) of Cd(II), Cu(II), Ni(II), Pb(II), Zn(II) in solutions prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of metal ions were optimized with respect to different experimental parameters using static and dynamic procedures in detail. The pH 4.0 was chosen as the optimum pH value for the separation of metal ions on the newly sorbent. Complete elution of the adsorbed metal ions from the nanometer SiO₂-morin was carried out using 2.0 mL of 0.5 mol L⁻¹ of HCl. Common coexisting ions did not interfere with the separation and determination at pH 4.0. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 22.36, 36.8, 40.37, 33.21 and 25.99 mg metal/g SiO₂-morin for Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), respectively. The time for 95% sorption for Cu(II) and Ni(II) and 70% sorption for Cd(II), Pb(II) and Zn(II) was less than 2 min. The relative standard deviation (RSD) of the method under optimum conditions was lower than 5.0% (n = 11). The procedure was validated by analyzing the certified reference river sediment material (GBW 08301, China), the results obtained were in good agreement with standard values. The nanometer SiO₂-morin was successfully employed in the separation and preconcentration of trace Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) from the biological and natural water samples yielding 75-folds concentration factor.     

Synthesis and crystal structure of Bi6.4Pb0.6P2O15.2: A new polymorph in the series Bi6+xM1−xP2O15+y

Bi_6.4Pb_0.6P₂O_15.2 is a polymorph of structures with the general stoichiometry Bi_6+xM_1−xP₂O_15+y. However, unlike previously published structures that consist of layers formed by edge sharing OBi₄ tetrahedra bridged by PO₄ and TO₆ (T=transition metal) tetrahedra and octahedra the title compound's structure is more complex. It is monoclinic, C2, a=19.4698(4) Å, b=11.3692(3) Å, c=16.3809(5) Å, β=101.167(1)°, Z=10. Single-crystal X-ray diffraction data were refined by least squares on F² converging to R₁=0.0387, wR₂=0.0836 for 7023 intensities. The crystal twins by mirror reflection across (001) as the twin plane and twin component 1 equals 0.74(1). Oxygen ions are in tetrahedral coordination to four metal ions and the O(BiPb)₄ units share corners to form layers that are part of the three-dimensional framework. Eight oxygen ions form a cube around the two crystallographically independent Pb ions. Pb-O bond lengths vary from 2.265(14) to 2.869(14) Å. Pairs of such cubes share an edge to form a Pb₃O₂₀ unit. The two oxygen ions from the unshared edges are part of irregular Bi polyhedra. Other oxygen ions of Bi polyhedra are part only of O(BiPb)₄ units, and some oxygen ions of the polyhedra are also part of PO₄ tetrahedra. One, two, three and or four PO₄ moieties are connected to the Bi polyhedra. Bi-O bond lengths ?3.1 Å vary from 2.090(12) to 3.07(3) Å. The articulations of Pb cubes, Bi polyhedra and PO₄ tetrahedra link into the three-dimensional structure.     

铜物种对Cu/Fe2O3水煤气变换反应催化剂性能的影响

采用共沉淀法制备了系列铜负载量不同的Cu/Fe₂O₃水煤气变换(WGS)催化剂,并考察了铜负载量对催化剂结构和水煤气变换反应性能的影响. 结果表明,Cu/Fe₂O₃催化剂呈现出良好的水煤气反应性能,当CuO质量分数为20%时,催化剂的WGS性能最优,250 ℃时CO转化率高达97.2%,同时热稳定性也最好. 运用X射线粉末衍射(XRD)、N₂物理吸脱附和H₂程序升温还原(H₂-TPR)等手段对Cu/Fe₂O₃催化剂的物相、织构特征及还原性能进行了表征,结果表明,CuFe₂O₄物种的存在极大地改善了催化剂的还原性能和WGS反应活性. 这是由于CuFe₂O₄特殊的尖晶石结构有利于Cu微晶的稳定;同时,CuFe₂O₄在低温下即被还原为单质铜,有利于促进催化剂体系中电子的转移. 此外,通过(NH₄)₂CO₃溶液处理,研究了独立相CuO对Cu/Fe₂O₃催化剂WGS反应性能的影响,结果发现,独立相CuO的存在,有利于H原子在各组分传递,从而促进催化剂的CuFe₂O₄的还原,改善Cu/Fe₂O₃催化剂的WGS反应性能.     

Removal of Cd(II) from Micro-Polluted Water by Magnetic Core-Shell Fe3O4@Prussian Blue

A novel core-shell magnetic Prussian blue-coated Fe₃O₄ composites (Fe₃O₄@PB) were designed and synthesized by in-situ replication and controlled etching of iron oxide (Fe₃O₄) to eliminate Cd (II) from micro-polluted water. The core-shell structure was confirmed by TEM, and the composites were characterized by XRD and FTIR. The pore diameter distribution from BET measurement revealed the micropore-dominated structure of Fe₃O₄@PB. The effects of adsorbents dosage, pH, and co-existing ions were investigated. Batch results revealed that the Cd (II) adsorption was very fast initially and reached equilibrium after 4 h. A pH of 6 was favorable for Cd (II) adsorption on Fe₃O₄@PB. The adsorption rate reached 98.78% at an initial Cd (II) concentration of 100 μg/L. The adsorption kinetics indicated that the pseudo-first-order and Elovich models could best describe the Cd (II) adsorption onto Fe₃O₄@PB, indicating that the sorption of Cd (II) ions on the binding sites of Fe₃O₄@PB was the main rate-limiting step of adsorption. The adsorption isotherm well fitted the Freundlich model with a maximum capacity of 9.25 mg·g⁻¹ of Cd (II). The adsorption of Cd (II) on the Fe₃O₄@PB was affected by co-existing ions, including Cu (II), Ni (II), and Zn (II), due to the competitive effect of the co-adsorption of Cd (II) with other co-existing ions.     

Synthesis and characterization of metal substituted AlxCr1−x(acetylacetonate)3 single-source precursors for their application to MOCVD of thin films

A detailed study, involving the synthesis of a single-source precursor containing two metal ions sharing the same crystallographic site, has been undertaken to elucidate the use of such a single-source precursor in a CVD process for growing thin films of oxides comprising these two metals, ensuring a uniform composition and distribution of metal ions. The substituted complexes Cr_1−xAl_x(acac)₃, where acac = acetylacetonate, have been prepared by a co-synthesis method, and characterized using UV–Vis spectroscopy, TGA/DTA measurements, and single crystal X-ray diffraction at low temperature. All the studied compositions crystallize in the monoclinic space group P2₁/c with Z = 4 in the unit cell. It was observed that the ratio (Al:Cr) of the site occupancy for the metal ions, obtained from single crystal refinement, is in agreement with the results obtained from complexometric titrations. All the solid state structures have the metal in an octahedral environment forming six-membered chelate rings. M–O acac bond lengths and disorder in the terminal carbon have been studied in detail for these substituted metal–organic complexes. One composition among these was chosen to evaluate their suitability as a single-source precursor in a LPMOCVD process (low-pressure metal–organic chemical vapour deposition) for the deposition of a substituted binary metal oxide thin film. The resulting thin films were characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy.     

Carbon Dioxide Reforming of Methane over Ni Catalysts Supported on Al2O3 Modified with La2O3, MgO, and CaO

The preparation of synthesis gas from carbon dioxide reforming of methane (CDR) has attracted increasing attention. The present review mainly focuses on CDR to produce synthesis gas over Ni/MO_x/Al₂O₃ (X = La, Mg, Ca) catalysts. From the examination of various supported nickel catalysts, the promotional effects of La₂O₃, MgO, and CaO have been found. The addition of promoters to Al₂O₃-supported nickel catalysts enhances the catalytic activity as well as stability. The catalytic performance is strongly dependent on the loading amount of promoters. For example, the highest CH₄ and CO₂ conversion were obtained when the ratios of metal M to Al were in the range of 0.04–0.06. In the case of Ni/La₂O₃/Al₂O₃ catalyst, the highest CH₄ conversion (96%) and CO₂ conversion (97%) was achieved with the catalyst (La/Al = 0.05 (atom/atom)). For Ni/CaO/Al₂O₃ catalyst, the catalyst with Ca/Al = 0.04 (atom/atom) exhibited the highest CH₄ conversion (91%) and CO₂ conversion (92%) among the catalysts with various CaO content. Also, Ni/MgO/Al₂O₃ catalyst with Mg/Al = 0.06 (atom/atom) showed the highest CH₄ conversion (89%) and CO₂ conversion (90%) among the catalysts with various Mg/Al ratios. Thus it is most likely that the optimal ratios of M to Al for the highest activities of the catalysts are related to the highly dispersed metal species. In addition, the improved catalytic performance of Al₂O₃-supported nickel catalysts promoted with metal oxides is due to the strong interaction between Ni and metal oxide, the stabilization of metal oxide on Al₂O₃ and the basic property of metal oxide to prevent carbon formation.     

Adsorptive Removal of Cd,Cu, Ni and Mn from Environmental Samples Using Fe3O4-Zro2@APS Nanocomposite: Kinetic and Equilibrium Isotherm Studies

In this study, Fe₃O₄-ZrO₂ functionalized with 3-aminopropyltriethoxysilane (Fe₃O₄-ZrO₂@APS) nanocomposite was investigated as a nanoadsorbent for the removal of Cd(II), Cu(II), Mn (II) and Ni(II) ions from aqueous solution and real samples in batch mode systems. The prepared magnetic nanomaterials were characterized using X-ray powder diffraction (XRD), scanning electron microscopy/energy dispersion x-ray (SEM/EDX) Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Factors (such as adsorbent dose and sample pH) affecting the adsorption behavior of the removal process were studied using the response surface methodology. Under optimized condition, equilibrium data obtained were fitted into the Langmuir and Freundlich isotherms and the data fitted well with Langmuir isotherms. Langmuir adsorption capacities (mg/g) were found to be 113, 111, 128, and 123 mg/g for Cd, Cu, Ni and Mn, respectively. In addition, the adsorption kinetics was analyzed using five kinetic models, pseudo-first order, pseudo-second order, intraparticle diffusion and Boyd models. The adsorbent was successfully applied for removal of Cd(II), Cu(II), Mn (II) and Ni(II) ions in wastewater samples.     

Sm0.5Sr0.5Co1−xNixO3−δ—A Novel Bifunctional Electrocatalyst for Oxygen Reduction/Evolution Reactions

The development of non-precious metal catalysts with excellent bifunctional activities is significant for air–metal batteries. ABO₃-type perovskite oxides can improve their catalytic activity and electronic conductivity by doping transition metal elements at B sites. Here, we develop a novel Sm_0.5Sr_0.5Co_1−xNi_xO_3−δ (SSCN) nanofiber-structured electrocatalyst. In 0.1 M KOH electrolyte solution, Sm_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ (SSCN82) with the optimal Co: Ni molar ratio exhibits good electrocatalytic activity for OER/ORR, affording a low onset potential of 1.39 V, a slight Tafel slope of 123.8 mV dec⁻¹, and a current density of 6.01 mA cm⁻² at 1.8 V, and the ORR reaction process was four-electron reaction pathway. Combining the morphological characteristic of SSCN nanofibers with the synergistic effect of cobalt and nickel with a suitable molar ratio is beneficial to improving the catalytic activity of SSCN perovskite oxides. SSCN82 exhibits good bi-functional catalytic performance and electrochemical double-layer capacitance.     

纳米复合固体超强酸SO42-/CoFe2O4的制备和表征

采用纳米化学制备技术合成了新型的纳米复合固体超强酸催化剂ＳＯ４＾２－／ＣｏＦｅ２Ｏ４。用ＸＲＤ、ＴＥＭ、ＸＰＳ、红外光谱和比表面测定等技术研究了该催化剂的结构形态,结果表明：所研制的ＳＯ４＾２－／ＣｏＦｅ２Ｏ４２催化剂为晶态纳米粒子（〈５０ｎｍ）,比表面积很大（１５７ｍ＾２．ｇ＾－１）,ＳＯ４＾２－与氧化物的金属离子呈无机齿螯合状配位化合物的结合形式。以乙酸乙酯合成为模型反应考究了该催化剂的催化活     

吸附相反应技术制备MnOx/CeO2/SiO2催化剂及其低温选择性催化还原Nox

采用吸附相反应技术制备得到了MnO_x/CeO₂/SiO₂催化剂,通过X 射线衍射（XRD）、透射电子显微镜（TEM）、高分辨透射电子显微镜（HRTEM）、紫外激光拉曼（Raman）等手段对催化剂进行了表征. HRTEM分析表明活性组分MnO_x与CeO₂都均匀分布在载体SiO₂表面;XRD分析表明Mn₃O₄特征峰随着CeO₂含量的增加逐渐减小至完全消失,CeO₂的加入降低了MnO_x的结晶程度,增加了MnO_x的分散性;Raman光谱表明催化剂表面的Mn离子能够进入CeO₂晶格,激发出空穴氧,随着CeO₂负载量的增加,催化剂氧空穴浓度先升高后降低.以NH₃为还原剂,考评催化剂的NO_x低温选择性催化还原（SCR）性能,催化剂催化活性随CeO₂负载量增加先升高后降低,与催化剂氧空穴浓度变化规律一致,说明催化剂活性受氧空穴浓度影响,氧空穴浓度升高,催化剂催化活性升高.     

One-Pot Facile Synthesis of Noble Metal Nanoparticles Supported on rGO with Enhanced Catalytic Performance for 4-Nitrophenol Reduction

In this study, reduced graphene oxide (rGO)-supported noble metal (gold, silver, and platinum) nanoparticle catalysts were prepared via the one-pot facile co-reduction technique. Various measurement techniques were used to investigate the structures and properties of the catalysts. The relative intensity ratios of I_D/I_G in rGO/Au, rGO/Ag, rGO/Pt, and GO were 1.106, 1.078, 1.047, and 0.863, respectively. The results showed the formation of rGO and that noble metal nanoparticles were decorated on rGO. Furthermore, the catalytic activities of the designed nanocomposites were investigated via 4-nitrophenol. The catalysts were used in 4-nitrophenol reduction. The catalytic performance of the catalysts was evaluated using the apparent rate constant k values. The k value of rGO/Au was 0.618 min⁻¹, which was higher than those of rGO/Ag (0.55 min⁻¹) and rGO/Pt (0.038 min⁻¹). The result proved that the rGO/Au catalyst exhibited a higher catalytic performance than the rGO/Ag catalyst and the rGO/Pt catalyst. The results provide a facile method for the synthesis of rGO-supported nanomaterials in catalysis.     

Electrocatalytic CO2 Reduction and H2 Evolution by a Copper (II) Complex with Redox-Active Ligand

The process of electrocatalytic CO₂ reduction and H₂ evolution from water, regarding renewable energy, has become one of the global solutions to problems related to energy consumption and environmental degradation. In order to promote the electrocatalytic reactivity, the study of the role of ligands in catalysis has attracted more and more attention. Herein, we have developed a copper (II) complex with redox-active ligand [Cu(L¹)₂NO₃]NO₃ (1, L¹ = 2-(6-methoxypyridin-2-yl)-6-nitro-1h-benzo [D] imidazole). X-ray crystallography reveals that the Cu ion in cation of complex 1 is coordinated by two redox ligands L¹ and one labile nitrate ligand, which could assist the metal center for catalysis. The longer Cu-O bond between the metal center and the labile nitrate ligand would break to provide an open coordination site for the binding of the substrate during the catalytic process. The electrocatalytic investigation combined with DFT calculations demonstrate that the copper (II) complex could homogeneously catalyze CO₂ reduction towards CO and H₂ evolution, and this could occur with great performance due to the cooperative effect between the central Cu (II) ion and the redox- active ligand L¹. Further, we discovered that the added proton source H₂O and TsOH·H₂O (p-Toluenesulfonic acid) could greatly enhance its electrocatalytic activity for CO₂ reduction and H₂ evolution, respectively.