多孔二元过渡金属纳米片阵列电极制备及电催化析氢研究

碱性电解液中,电解水析氢的H2O解离过程非常缓慢,造成析氢反应较高的过电位和Tafel效率。选择具有本征高析氢活性的合金催化剂与水解离中心-过渡金属氧化物复合,并进一步优化复合物形貌结构,被证明是解决这个科学问题的重要策略。本文报道一例新颖的二元过渡金属纳米片阵列自支撑电极（MoO3-x-MoNi4@NF）, 多孔MoO3-x纳米片阵列均匀生长在泡沫镍电极表面,纳米片表面镶嵌着MoNi4合金纳米颗粒,多孔的纳米片阵列使得催化剂具有高的比表面积（57 m2/g）和丰富的活性位点。在碱性电解液中（1 M KOH）,MoO3-x-MoNi4@NF仅需要过电位30mV就能达到10 mA cm-2电流密度,如此低的过电位超过了贵金属催化剂20% Pt/C (32 mV)。同时,MoO3-x-MoNi4@NF具有超低的Tafel斜率,仅为31 mV dec-1,如此低的Tafel斜率得益于Ni-Mo合金与MoO3-x之间的协同催化剂作用的发挥,MoO3-x可以有效促进H2O解离并释放Hads,MoNi4纳米颗粒作为Hads吸脱附位点可以促进H2生成,这使得该催化剂有望替代贵金属铂用作碱性电催化析氢领域。     

Annealing temperature dependent catalytic water oxidation activity of iron oxyhydroxide thin films

Nanostructured iron oxyhydroxide(Fe OOH) thin films have been synthesized using an electrodeposition method on a nickel foam(NF) substrate and effect of air annealing temperature on the catalytic performance is studied. The as-deposited and annealed thin films were characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS), field emission scanning electron microscopy(FE-SEM) and linear sweep voltammetry(LSV) to determine their structural, morphological, compositional and electrochemical properties, respectively. The as-deposited nanostructured amorphous Fe OOH thin film is converted into a polycrystalline Fe_2O_3 with hematite crystal structure at a high temperature. The Fe OOH thin film acts as an efficient electrocatalyst for the oxygen evolution reaction(OER) in an alkaline 1 M KOH electrolyte. The film annealed at 200 °C shows high catalytic activity with an onset overpotential of 240 m V with a smaller Tafel slope of 48 m V/dec. Additionally, it needs an overpotential of 290 mV to the drive the current density of 10 m A/cm~2 and shows good stability in the 1 M KOH electrolyte solution.     

One-step synthesis of Fe-Ni hydroxide nanosheets derived from bimetallic foam for efficient electrocatalytic oxygen evolution and overall water splitting

For the first time, the Fe-Ni LDH nanosheets were prepared through simple one-step hydrothermal treatment of Fe-Ni bimetallic foam both as the substrate and Fe/Ni sources. The ratio of Ni/Fe elements played the important role in realizing the optimal catalytic activities for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). An alkaline water electrolyzer was constructed with the Fe-Ni hydroxide nanosheets/Fe-Ni alloy foam-60% Fe as anode and Ni(OH)₂/Fe-Ni alloy foam-25% Fe as cathode, which displays superior electrolytic performance (affording 10 mA/cm² at 1.62 V) and lasting durability.     

Nickel-iron borate coated nickel-iron boride hybrid for highly stable and active oxygen evolution electrocatalysis

The development of efficient and cost-effective electrocatalysts toward anodic oxygen evolution reaction (OER) is crucial for the commercial application of electrochemical water splitting. As the most promising electrocatalysts, the OER performances of nickel-iron-based materials can be further improved by introducing metalloid elements to modify their electron structures. Herein, we developed an efficient hybrid electrocatalyst with nickel-iron boride (NiFeB) as core and amorphous nickel-iron borate (NiFeB_i) as shell (NiFeB@NiFeB_i) via a simple aqueous reduction. The obtained NiFeB@NiFeB_i exhibits a small overpotential of 237 mV at 10 mA/cm² and Tafel slope of 57.65 mV/dec in 1.0 mol/L KOH, outperforming most of the documented precious-metal-free based electrocatalysts. Benefiting from the in situ formed amorphous NiFeBi layer, it shows excellent stability toward the oxygen evolution reaction (OER). These findings might provide a new way to design advanced precious-metal-free electrocatalysts for OER and the application of electrochemical water splitting.     

Imine Gels Based on Ferrocene and Porphyrin and Their Electrocatalytic Property

A series of porphyrin‐based imine gels have been synthesized via dynamic covalent gelation between 5,10,15,20‐tetra(4‐aminophenyl)‐21H,23H‐porphyrin (H₂TAPP) derivatives and various aldehyde compounds. The porphyrin‐ferrocene imine gels based on MTAPP (M=H₂, Ni²⁺, Co²⁺, Pd²⁺ and Zn²⁺) and ferrocene‐1,1′‐dicarbaldehyde (NA) display efficient HER, OER and ORR activities in alkaline media. Among the gels, CoTAPP‐NA shows an HER current density of 10 mA cm^?2 at low overpotential of 470 mV and small Tafel slope of 110 mV decade^?1 in alkaline media. CoTAPP‐NA also exhibits OER catalytic activity with low overpotential (416 mV for 10 mA cm^?2). CoTAPP‐NA shows ability in overall water splitting in alkaline media. In addition, CoTAPP‐NA exhibits onset potential (E_p) of 0.95 V and half‐wave potential (E_1/2) of 0.84 V in 1.0 mol L^?1 KOH solution for oxygen reduction. Moreover, the gel catalyst shows good stability.     

基于磺酰基杯[4]芳烃的Co16笼簇的合成、结构及电化学性质

以氯化钴、 对叔丁基磺酰杯[4]芳烃(H₄TC4A-SO₂)和非对称性3-(1H-四唑-5-基)苯甲酸(H₂L)为原料, 通过溶剂热法合成了一个具有四面体配位笼结构的16核化合物[Co₁₆(TC4A-SO₂)₄(OH)₄(L)₈]·[(C₈H₂₀N)(C₄H₁₂N)₂(C₂H₈N)]·solvent(Co₁₆-TC4A-SO₂). 采用X射线单晶衍射、 X射线粉末衍射、 热重分析、 红外光谱方法对配合物进行了表征. 将Co₁₆-TC4A-SO₂笼簇直接负载到碳纸上(Co₁₆-TC4A-SO₂/CP)用作工作电极, 其对析氧反应(OER)展现出较好的催化性能. 在1 mol/L KOH中, Co₁₆-TC4A-SO₂/CP在343.8 mV的过电位下达到10.0 mA/cm ²电流密度, Tafel斜率为79.31 mV/dec, 并且在20.0 mA/cm ²电流密度下表现出长达48 h的催化稳定性.     

Controlled Synthesis of 3D Flower‐like Ni2P Composed of Mesoporous Nanoplates for Overall Water Splitting

Developing efficient non‐noble metal and earth‐abundant electrocatalysts with tunable microstructures for overall water splitting is critical to promote clean energy technologies for a hydrogen economy. Herein, novel three‐dimensional (3D) flower‐like Ni₂P composed of mesoporous nanoplates with controllable morphology and high surface area was prepared by a hydrothermal method and low‐temperature phosphidation as efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with the urchin‐like Ni_x P_y , the 3D flower‐like Ni₂P with a diameter of 5 μm presented an efficient and stable catalytic performance in 0.5 m H₂SO₄, with a small Tafel slope of 79 mV dec⁻¹ and an overpotential of about 240 mV at a current density of 10 mA cm⁻² with a mass loading density of 0.283 mg cm⁻². In addition, the catalyst also exhibited a remarkable performance for the OER in 1.0 m KOH electrolyte, with an overpotential of 320 mV to reach a current density of 10 mA cm⁻² and a small Tafel slope of 72 mV dec⁻¹. The excellent catalytic performance of the as‐prepared Ni₂P may be ascribed to its novel 3D morphology with unique mesoporous structure.     

Flower-like Fe-Co-M (M=S,O, P and Se) Nanosheet Arrays Grown on Nickel Foam as High-efficiency Bifunctional Electrocatalysts

The development of highly efficient, inexpensive, abundant and non-precious metal electrocatalysts is the lifeblood of the hydrogen production industry, especially the hydrogen production industry by electrolysis of water. A Fe-Co-S/NF bifunctional electrocatalyst with nanoflower-like structure was synthesized on three-dimensional porous nickel foam through one-step hydrothermal and one-step high-temperature sulfuration operations, and the material displays high-efficiency electrocatalytic performance. As a catalyst for the hydrogen evolution reaction, Fe-Co-S/NF can drive a current density of 10 mA/cm² at an overpotential of 143 mV with a Tafel slope of 80.2 mV/dec. When it was used as an oxygen evolution reaction catalyst, it exhibits good OER reactivity with a low Tafel slope (82.6 mV/dec) and with requiring only 117 mV overpotential to drive current densities up to 50 mA/cm². In addition, the Fe-Co-S/NF//Fe-Co-S/NF electrolytic cell was assembled, an electrolysis voltage of 1.64 V is required to drive a current density of 50 mA/cm², which is one of the most active catalysts reported so far. This work indicates that the introduction of S, P and Se treating processes could effectively improve electrical conductivity of the material and enhance the catalytic activity of the material. This work offers an effective and convenient method for improving the morphology of the catalyst, increasing the surface area of the catalyst and developing high-efficiency and low-cost catalysts.     

Highly exposed NiFeOx nanoclusters supported on boron doped carbon nanotubes for electrocatalytic oxygen evolution reaction

The development of efficient and cost-effective electrocatalysts for oxygen evolution reaction (OER) is crucial for the overall water splitting. Herein, we prepared a highly exposed NiFeO_x ultra-small nanoclusters supported on boron-doped carbon nonotubes catalyst, which achieves a 10 mA/cm² anodic current density at a low overpotential of 213 mV and the Tafel slope of 52 mV/dec in 1.0 mol/L KOH, superior to the pristine NiFeO_x-CNTs and other state-of-the-art OER catalysts in alkaline media. A combination study (XPS, sXAS and XAFS) verifies that the local atomic structure of Ni and Fe atoms in the nanoclusters are similar to NiO and Fe₂O₃, respectively, and the B atoms which are doped into the crystal lattice of CNTs leads to the optimization of Ni 3d e_g orbitals. Furthermore, in-situ X-ray absorption spectroscopies reveal that the high valence state of Ni atoms are served as the real active sites. This work highlights that the precise control of highly exposed multicomponent nanocluster catalysts paves a new way for designing highly efficient catalysts at the atomic scale.     

Single-crystalline layered double hydroxides with rich defects and hierarchical structure by mild reduction for enhancing the oxygen evolution reaction

The oxygen evolution reaction(OER) with sluggish reaction kinetics and large overpotential is the critical reaction in water splitting that is promising for energy storage and conversion. Layered double hydroxides(LDHs), due to their unique lamellar structure and flexibility of chemical component, are very competing material candidates for OER. Herein, the morphology structure and the electronic structure of LDHs were simultaneously tuned to improve the OER catalytic activity by mild solvothermal reduction using ethylene glycol. The increased surface area, the introduction of oxygen vacancies and the construction of hierarchical structure greatly enhanced the electro-catalytic activity of LDHs for OER. The as-prepared LDHs showed a lower over-potential as low as 276 mV at a current density of 10 mA cm~(-2), and a small Tafel slope of 40.3 mV dec~(-1) accompanied with good stability. This work provides an efficient way to the design and optimization of advanced catalysts in the future.     

无电沉积硼化镍材料对水氧化的电催化性能

通过无电沉积/化学镀的方法分别制得石墨烯(Graphene)、 镍网(Ni foam, NF)、 钛网(Ti mesh, TM)、 碳布(Carbon cloth, CC)负载的硼化镍材料. 其中在石墨烯基底上生长的硼化镍层由规则的纳米颗粒构成, 且均匀致密. 对几种材料在碱性条件下(1.0 mol/L KOH电解质中)的水氧化电催化性能进行了研究, 结果表明, 石墨烯基底上生长的硼化镍材料(NiB_x/graphene)具有最佳的水氧化电催化性能. 电流密度达到10 mA/cm²时的过电位仅为277 mV, 相应的Tafel斜率为57 mV/dec. 对石墨烯负载的硼化镍材料进行烧结, 测得过电位为330 mV, 与未烧结的样品相比电催化活性下降. 该方法所制的石墨烯负载的硼化镍材料兼具高电催化活性和稳定性, 为低成本、 高效率的水氧化非贵金属电催化剂的制备提供了新思路.     

The oxygen evolution reaction on cobalt: Part II. Transient measurements

Open-circuit overpotential decays on an aged cobalt electrode in the oxygen evolution range in 6 M KOH show different slopes for two overpotential regions. These slopes are lower than the Tafel slope in the same region: Tafel slopes of ～100 and ～40 mV/dec, at high and low overpotentials, respectively. compared to decay slopes of ～?60 and ～?20 to ?30 mV/dec. For a fresh cobalt electrode a decay slope of ～?40 mV/dec is found at high overpotentials. From impedance measurements during a decay it is concluded that the electrode capacitance cannot account for the decay curves obsered. By means of steady-state potentiostatic impedance measurements (with stabilization times > 24 h) it is found that the differential Tafel slope remains constant at ～40–50 mV/dec and differs considerably from the Tafel slope at high overpotentials, ～100 mV/dec. Galvanostatic pulse experiments give evidence of the presence of CoO₂ in the oxide layer.Two models which may explain the observed experimental results are analysed. Both include a potential-dependent (extra) process which is fixed by the amount of CoO₂ at the surface. In one model, CoO₂ is responsible for partial surface blockage (parallel process); in the other model, CoO₂ controls the conductivity of the top layer of the oxide layer on the electrode.     

Gold nanoparticles decorated covalent organic polymer as a bimodal catalyst for total water splitting and nitro compound reduction

The design and construction of a bimodal catalyst with magnificent performance and high stability is a debatable one for total water splitting and nitro compound reduction. Herein, we report the synthesis of a covalent organic polymer network based on 1,4-phenylenediamine based covalent organic polymer (PD-COP) and its decoration with Au nanoparticles (Au NPs) as well as their confirmation using various analytical and surface techniques. The electrocatalytic activity toward total water-splitting reaction (OER and HER) in KOH solution (1.0 M) was investigated. In addition, the reduction of aromatic nitro compounds (4-nitrophenol (4-NP) and 2-nitroaniline (2-NA)) was carried out in the presence of NaBH₄. Among the different electrocatalysts (PD-COP, Au@PD-COP-I, Au@PD-COP-II, Au@PD-COP-III and Au@PD-COP-IV) studied in this work, the Au@PD-COP-II demands a low overpotential of 288 mV and 184 mV to attain a 50-mA/cm² geometrical current density with a lowest Tafel slope value of 56 and 85 mV/dec for OER and HER respectively. From the OER and HER phenomenal activity, a two-electrode system was constructed, and it needs a cell voltage of 1.615 V to conquer a current density of 10 mA/cm² with outstanding stability for 34 h. The high electroactivity of Au@PD-COP-II may be allied with the presence of innumerable redox-active sites and high electrochemical active surface area (ECSA) towards effective water electrolysis. Further, the catalytic activity performed towards the reduction of 4-NP to 4-aminophenol (4-AP) and 2-NA to o-PDA (o-phenylenediamine), Au@PD-COP-II showed good catalytic activity with a reduction time of 20 and 14 min respectively.     

Surface oxidized iron-nickel nanorods anchoring on graphene architectures for oxygen evolution reaction

Surface oxidized iron-nickel nanorods coupling with reduced graphene architectures (FeNi-O-rGA) are successfully constructed via hydrothermal, freeze-drying, and thermal activation approaches. The hierarchical structure can provide lots of pathways for fast ion diffusion and charge transfer, and expose abundant catalytic sites. Meanwhile, the activity of FeNi-O-rGA is boosted by the optimized metal-oxygen bond strength in FeNi₃ alloys. Partial oxidized FeNi nanorods are strongly coupled with rGA by the formation of metal-O-C bonds, which can impede the aggregation of FeNi₃ alloys and increase the utilization of active sites. The special structure and partially oxidized FeNi nanorods for FeNi-O-rGA can result in excellent OER activity and catalytic stability. Only 215 mV of overpotential is required to drive the current density of 10 mA/cm² as well as the Tafel slope of 50.9 mV/dec in 1 mol/L KOH. The change of surface chemistry of FeNi-O-rGA is confirmed by XPS after the OER test, which indicates the highly catalytic stability of FeNi-O-rGA due to the formation of intermediate metal oxyhydroxide.     

脊椎状NiCo2O4纳米棒的制备及其析氧和氧还原性能研究

以水热法并进一步焙烧合成脊椎状NiCo₂O₄纳米棒,通过透射电子显微镜（TEM）、X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）和热重分析仪（TG）等来表征其结构形态及热稳定性.采用线性扫描法（LSV）、循环伏安（CV）研究所制备催化剂的在玻碳和旋转圆盘电极上的电催化活性：在0.1 mol·L^-1 KOH溶液中的电催化析氧反应（OER）和电催化氧还原反应（ORR）.研究结果表明,所制备的脊椎状NiCo₂O₄纳米棒有大量的不饱和态,200℃焙烧制备的脊椎状NiCo₂O₄纳米棒析氧过电位最小可达309 mV,Tafel斜率145.6 mV/dec,其氧还原极限电流密度在1600 rmp可达到5.095 mA·cm^-2,电子转移数在3.2~3.8之间,接近四电子转移机理,其优良电化学性能可能是由于暴露了更多的边缘缺陷的缘故.     

A general bimetal-ion adsorption strategy to prepare nickel single atom catalysts anchored on graphene for efficient oxygen evolution reaction

Single-atom catalysts (SACs) supported on two-dimensional (2D) materials are highly attractive for maximizing their catalytic activity.However,graphene based SACs are primarily bonded with nitrogen and carbon sites,resulting in poor performance for the oxygen evolution reaction (OER).Herein,we develop a general bimetal-ion adsorption strategy for the synthesis of individually dispersed Ni SACs anchored on the oxygenated sites of ultrathin reduced graphene oxide as efficient OER electrocatalysts.The resultant Ni SACs for OER in alkaline electrolyte exhibit a highly stable overpotential of 328 mV at the current density of 10 mA cm~(-2),and Tafel slope of 84 mV dec~(-1) together with long-term durability and negligible degradation for 50 h,which is greatly outperform its counterparts of nitrogen bonded Ni SACs (564 mV,364 mV dec~(-1)) and Ni(OH)_2 nanoparticles anchored on graphene (450 mV,142 mV dec~(-1)),and most reported Ni based OER electrocatalysts.Furthermore,the extended X-ray absorption fine structure at the Ni K-edge and theoretical simulation reveal that the nickel-oxygen coordination significantly boost OER performance.Therefore,this work will open numerous opportunities for creating novel-type 2D SACs via oxygen-metal bonding as highly robust OER catalysts.     

Water oxidation electrocatalyzed by an efficient Mn3O4/CoSe2 nanocomposite

The design of efficient, cheap, and abundant oxygen evolution reaction (OER) catalysts is crucial to the development of sustainable energy sources for powering fuel cells. We describe here a novel Mn(3)O(4)/CoSe(2) hybrid which could be a promising candidate for such electrocatalysts. Possibly due to the synergetic chemical coupling effects between Mn(3)O(4) and CoSe(2), the constructed hybrid displayed superior OER catalytic performance relative to its parent CoSe(2)/DETA nanobelts. Notably, such earth-abundant cobalt (Co)-based catalyst afforded a current density of 10 mA cm(-2) at a small overpotential of ~0.45 V and a small Tafel slope down to 49 mV/decade, comparable to the best performance of the well-investigated cobalt oxides. Moreover, this Mn(3)O(4)/CoSe(2) hybrid shows good stability in 0.1 M KOH electrolyte, which is highly required to a promising OER electrocatalyst.     

Fe‐Doped Ni3C Nanodots in N‐Doped Carbon Nanosheets for Efficient Hydrogen‐Evolution and Oxygen‐Evolution Electrocatalysis

Uniform Ni₃C nanodots dispersed in ultrathin N‐doped carbon nanosheets were successfully prepared by carburization of the two dimensional (2D) nickel cyanide coordination polymer precursors. The Ni₃C based nanosheets have lateral length of about 200 nm and thickness of 10 nm. When doped with Fe, the Ni₃C based nanosheets exhibited outstanding electrocatalytic properties for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). For example, 2 at % Fe (atomic percent) doped Ni₃C nanosheets depict a low overpotential (292 mV) and a small Tafel slope (41.3 mV dec⁻¹) for HER in KOH solution. An outstanding OER catalytic property is also achieved with a low overpotential of 275 mV and a small Tafel slope of 62 mV dec⁻¹ in KOH solution. Such nanodot‐incorporated 2D hybrid structures can serve as an efficient bifunctional electrocatalyst for overall water splitting.     

自支撑NiFe LDH-MoSx集成电极在工业电解水条件下实现高效电解水

化石燃料的枯竭和不断增长的能源需求给人类带来巨大的挑战,加之能源消耗过程带来的环境问题使得开发清洁可再生绿色能源迫在眉睫.氢能具有零排放、可再生、能量高和来源广等特点,且可通过化石能源和电解水制取,是未来人类最理想的替代能源之一.相较于化石能源制氢,电解水制氢被认为是一种最有前途的清洁制氢技术,能够将可再生能源(例如太阳能和风能)产生的剩余电能以化学能的形式存储起来.电解水反应由发生在阴极的析氢反应与发生在阳极的析氧反应组成.其中,析氧反应涉及多个质子和电子转移,反应动力学缓慢严重限制了其水分解的整体效率.为满足实际应用,亟待开发低成本、高催化活性和在工业电解条件(60～80℃,20％～30％ KOH,400 mA·cm-2)下长期稳定性强等特性的析氧催化剂.本文报道了一种用于析氧反应的自支撑泡沫镍铁自支撑的镍铁层状双金属氢氧化物-二硫化钼(NiFe LDH-MoSx/INF)集成电极,在正常碱性测试条件(25℃,1 M KOH)和模拟工业电解条件(65 ° C,5 M KOH)下均表现出优异的催化性能.优化后的电极在一般碱性测试条件下,过电势仅需195和290 mV即可达到100和400 mA·cm-2的电流密度.在模拟工业电解条件下达到相同的电流密度,过电势只需156和201 mV.在两种条件下进行长期稳定性测试,催化剂均未观察到明显的失活现象.在两电极体系(NiFe LDH-MoSx/INF ‖ 20％Pt/C)全解水测试中,达到100 mA·cm2的电流密度仅需1.72 V的电压.还使用NiFe LDH-MoSx/INF作为阳极催化剂构建膜电极并评价其阴离子交换膜电解水的性能:在400 mA·cm-2的电流密度下能量转换效率(60℃,1 M KOH)为71.8％.综上,原位生长策略保证了此类电极的长期稳定性.硫化基底的存在可以控制NiFe LDH的生长厚度,从而提高集成电极的整体导电性.另外,MoSx的引入进一步调节了NiFe LDH的电子结构,进而优化了反应中间体的吸附能及状态.在模拟工业操作条件下进行的电化学测试进一步证实了多孔三维自支撑NiFe LDH-MoSx/INF集成电极具有在工业电解水中大规模应用的前景.本文为合理设计用于工业阴离子交换膜水电解的非贵金属析氧催化剂提供新的策略.     

基于Cu(Ⅱ) Tricine配合物制备氧化铜薄膜及其电催化水氧化活性

众所周知, 传统化石燃料的大量使用不仅导致严重的环境污染和温室效应, 而且化石能源本身也面临着枯竭的危机.所以, 探索全新的、环境友善的、可持续发展的能源载体一直备受国内外科研工作者的关注. 氢能是一种清洁的可再生能源, 是有潜力的化石能源替代品. 水分解是一种有效的、理想的产氢途径, 然而水氧化反应是多质子多电子传递的过程, 是制约整个水分解过程的瓶颈. 目前, 基于贵金属(铱和钌)分子和氧化物的电催化剂已经被报道很多, 并且可以保持很好的催化活性; 但是, 这一类催化剂差的稳定性、昂贵的价格和少的地壳含量等因素严重制约了其大规模实际应用. 因此, 开发基于非贵金属(钴、镍、铁、铜、锰)的新型电催化剂材料是解决该问题的唯一出路, 但要保证电催化剂的高活性和好的稳定性仍面临着诸多挑战.在众多的非贵金属中, 铜是一种来源广泛的金属, 而且铜对生物体毒性较小. 由于铜具有良好的配位化学和多重的氧化还原特性, 近年来, 很多基于铜的水氧化电催化剂被开发和研究.我们在含有1.0 mmol/L Cu2+和2.0 mmol/L Tris配体的磷酸缓冲溶液(0.2 mol/L, pH = 12.0)中, 采用1.15 V vs. NHE恒电位电沉积的方法, 在ITO导电玻璃上制备出基于铜的水氧化催化剂薄膜(Cu-tricine). 对得到的催化剂薄膜进行扫描电镜(SEM)测试, 该催化剂均匀负载在ITO表面, 厚度大约是1.4 μm. 为了更加深入研究Cu-Tricine催化剂薄膜, 采用透射电子显微镜(TEM)和X射线衍射(XRD)对Cu-tricine催化剂进行表征, 结果表明, 该催化剂薄膜是一种结晶度较差的无定形材料. 同时, 为了研究催化剂薄膜的元素组成及其所处状态, 对催化剂进行了能量散射X射线能谱(EDX)和X射线光电子能谱(XPS)测试, 结果表明, 该催化剂由铜和氧元素组成, 并且铜是以正二价存在. 由高分辨O 1s XPS谱图分析结果可以推测, Cu-Tricine催化剂可能是由氧化铜和氢氧化铜组成. Cu-tricine催化剂的水氧化活性是在0.2 mol/L的磷酸缓冲溶液(pH =12.0)中进行测试, 从塔菲尔曲线中可以得出, 该催化剂达到1.0 mA/cm2的催化电流密度所需的过电位是395 mV, 塔菲尔斜率为46.7 mV/decade. 此外, 在1.15 V vs. NHE的电位下, 在10 h的电解过程中, Cu-tricine催化剂薄膜可以将催化电流密度一直保持在7.5 mA/cm2, 并且得到的法拉第效率为99%.