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1.
Halide perovskites show incredible photovoltaic power conversion efficiency coupled with several hundreds of hours of device stability. However, their stability is poor in aqueous electrolyte media. Reported here is a vacancy ordered halide perovskite, Cs2PtI6, which shows extraordinary stability under ambient conditions (1 year), in aqueous media of extreme acidic (pH 1), basic (pH 13), and under electrochemical reduction conditions. It was employed as an electrocatalyst and photoanode for hydrogen production and water oxidation, respectively. The catalyst remains intact for at least 100 cycles of electrochemical cycling and six hours of hydrogen production at pH 1. Cs2PtI6 was employed as a photoanode for PEC water oxidation, and the material displayed a photocurrent of 0.8 mA cm?2 at 1.23 V (vs. RHE) under simulated AM1.5G sunlight. Using constant voltage measurement, Cs2PtI6 exhibited over 12 hours of PEC stability without loss of performance.  相似文献   

2.
Most CdTe photoanodes and photocathodes show positive and negative photocurrent onset potentials for water oxidation and reduction, respectively, and are thus unable to drive photoelectrochemical (PEC) water splitting without external applied biases. Herein, the activity of a CdTe photoanode having an internal p‐n junction during PEC water oxidation was enhanced by applying a CdCl2 annealing treatment together with surface modifications. The resulting CdTe photoanode generated photocurrents of 1.8 and 5.4 mA cm?2 at 0.6 and 1.2 VRHE, respectively, with a photoanodic current onset potential of 0.22 VRHE under simulated sunlight (AM 1.5G). The CdCl2 annealing increased the grain sizes and lowered the density of grain boundaries, allowing more efficient charge separation. Consequently, a two‐electrode tandem PEC cell comprising a CdTe‐based photoanode and photocathode split water without any external bias at a solar‐to‐hydrogen conversion efficiency of 0.51 % at the beginning of the reaction.  相似文献   

3.
Metal halide perovskites, primarily used as optoelectronic devices, have not been applied for electrochemical conversion due to their insufficient stability in moisture. Herein, two bismuth-based perovskites are introduced as novel electrocatalysts to convert CO2 into HCOOH in aqueous acidic media (pH 2.5), exhibiting a high Faradaic efficiency for HCOOH of >80 % in a wide potential range from −0.75 to −1.25 V. Their structural evolution against water was dynamically monitored by in situ spectra. Theoretical calculations further reveal that the formation of intermediate OCHO* on bismuth sites of Cs3Bi2Br9(111) play a pivotal role toward HCOOH production, which has a lower energy barrier than that on Cs2AgBiBr6(001) surfaces. Significantly, CO2 reacts with protons instead of water which can enhance CO2 reduction rate and suppress hydrogen evolution by avoiding carbonate formation in acidic electrolytes. This work paves the way for the extensive investigation of halide perovskites in aqueous systems.  相似文献   

4.
刘志锋  鲁雪 《催化学报》2018,39(9):1527-1533
光电化学分解水制氢可以一并解决环境问题和能源危机,因而成为研究热点.由于TiO_2 禁带宽度较大,不能有效吸收太阳光中的可见光,使光电化学分解水制氢的应用受限.g-C_3N_4的禁带宽度约为2.7 e V,能有效吸收可见光,但g-C_3N_4薄膜制备研究较少.我们通过热聚缩合法直接在FTO导电玻璃上制备出g-C_3N_4薄膜,发现其光电化学分解水制氢稳定性不高,选择易制备的TiO_2 作为保护层可以提高g-C_3N_4的耐用性.此外,为提高g-C_3N_4光生电子空穴对的分离能力,依靠Co-Pi对光生空穴的捕获作用而将其覆盖在最外层.因此本文首次制备一种新型的g-C_3N_4/TiO_2 /Co-Pi光阳极用于光电化学分解水制氢,其中g-C_3N_4用作光吸收层,TiO_2 用作保护层,Co-Pi用作空穴捕获层.并在此基础上,通过扫描电子显微镜(SEM),X射线衍射(XRD),紫外可见光谱(UV-Vis)等手段研究了g-C_3N_4/TiO_2 /Co-Pi光阳极的形貌特征和光电化学性能.SEM、EDS和XRD结果表明,g-C_3N_4/TiO_2 /Co-Pi光阳极被成功制备在了FTO导电玻璃上,厚度约为3μm.UV-Vis测试表明,g-C_3N_4的光吸收边约为470 nm,可以有效地吸收可见光,并且g-C_3N_4的框架结构使光多次反射折射增加了光的捕获能力,由此可见,g-C_3N_4能够发挥很好的光吸收层作用.通过对g-C_3N_4光阳极,g-C_3N_4/TiO_2 光阳极和g-C_3N_4/TiO_2 /Co-Pi光阳极的电流电压测试发现,g-C_3N_4/TiO_2 光阳极的光电流密度小于g-C_3N_4光阳极,而g-C_3N_4/TiO_2 /Co-Pi光阳极的光电流密在可逆氢电极1.1 V下达到了0.346 mA?cm–2,约为单独g-C_3N_4光阳极的3.6倍.这说明Co-Pi是提升g-C_3N_4光电化学性能的主要因素.电化学阻抗测试结果发现,g-C_3N_4/TiO_2 /Co-Pi光阳极的界面电荷转移电阻小于g-C_3N_4光阳极的,这表明g-C_3N_4/TiO_2 /Co-Pi光阳极界面处载流子转移较快,同时也能促进内部光生电子空穴对的分离,整体性能的提高应该主要归因于Co-Pi对光生空穴的捕获作用.恒电压时间测试展示出g-C_3N_4/TiO_2 /Co-Pi光阳极的光电流密度在2 h测试过程中没有明显下降,表明g-C_3N_4/TiO_2 /Co-Pi光阳极是相当稳定的,具有良好的耐用性,归因于TiO_2 和Co-Pi的共同保护作用,主要归因于TiO_2 层对FTO导电玻璃上的g-C_3N_4薄膜保护,从电化学沉积Co-Pi到所有测试结束.总体而言,g-C_3N_4/TiO_2 /Co-Pi光阳极加强的光电化学性能归因于以下几个因素:(1)g-C_3N_4优异的光吸收能力;(2)TiO_2 稳定的保护提升了g-C_3N_4薄膜的耐用性;(3)Co–Pi对光生空穴的捕获有效促进了光生电子空穴对的分离.  相似文献   

5.
Hematite(α-Fe_2O_3) is a promising photoanode for photoelectrochemical(PEC) water splitting.However,the severe charge recombination and sluggish water oxidation kinetics extremely limit its use in photohydrogen conversion.Herein,a co-activation strategy is proposed,namely through phosphorus(P)doping and the loading of CoAl-layered double hydroxides(CoAl-LDHs) cocatalysts.Unexpectedly,the integrated system,CoAl-LDHs/P-Fe_2O_3 photoanode,exhibits an outstanding photocurrent density of 1.56 mA/cm~2 at 1.23 V(vs.reversible hydrogen electrode,RHE),under AM 1.5 G,which is 2.6 times of pureα-Fe_2O_3.Systematic studies reveal that the remarkable PEC performance is attributed to accelerated surface OER kinetics and enhanced carrier separation efficiency.This work provides a feasible strategy to enhance the PEC performance of hematite photoanodes.  相似文献   

6.
K2ThI6, Rb2ThI6, Cs2ThI6 and Cs2TiI6 could be prepared from the reactions of alkali metal iodides with ThI4 and TiI4. By precipitation with an excess of alkali metal iodide, Rb2OsI6, Cs2OsI6, K2PtI6 and Rb2PtI6 were obtained from acid solutions of the hexaiodometallate(IV) anions, Rb2OsBr6 was synthesized in a similar way from the corresponding bromine compounds.The formation of the 4th group hexaiodometallates was investigated by DTA. The thermal stability of the complex salts was determined.  相似文献   

7.
Preparation and Crystal Structure of PtI3, a Mixed-valence Platinum (II, IV) Iodide PtI3 was obtained by thermal decomposition of PtI4 in a closed system at 300°C and 8 atm iodine pressure. Single crystals were formed by the reaction of PtI4 with aqueous solutions of KI and I2 at 270°C. The crystal structure of the monoclinic compound (a = 673.5(2) pm; b = 1206.1(4) pm; c = 1331.3(5) pm; β = 101.25(6)°; Z = 8; space group C2/c-C2h6) contains square planar PtI4 and octahedral PtI6 groups which are connected by common edges to chains.  相似文献   

8.
《中国化学快报》2020,31(10):2661-2667
This study aimed to construct a photoelectrocatalytic (PEC) reaction system based on the self-made reduced TiO2 NTAs (r-TNAs) photoanode and activated carbon/Polytetrafluoroethylene (AC/PTFE) cathode. It would be observed clearly that the degradation rate constant of carbamazepine (CBZ) over r-TNAs(photoanode)-AC/PTFE(cathode) PEC system (0.04961 min−1) was even higher than that of r-TNAs(photoanode)-Pt(cathode) PEC system (0.04602 min−1) with the assistance of visible light irradiation and +0.4 V external potential. Besides, in order to obtain optimized conditions, the influence of key parameters such as pH value, electric current density and electrolyte concentration were studied. Most importantly, photoelectrochemical (PECH) properties, reactive oxide species contribution, OH formation rate and CBZ degradation pathway were determined. The results illustrated that the excellent PEC degradation performance depended on the excellent photocatalytic property of r-TNAs photoanode and electron transfer property of photoelectrodes in r-TNAs(photoanode)-AC/PTFE(cathode) PEC system. Therefore, the study demonstrated that the r-TNAs(photoanode)-AC/PTFE(cathode) PEC system could be expected to replace metal-catalyzed cathodes depending on its excellent PEC performance activity and low cost as well as the reaction system possessed objective and practical application prospect.  相似文献   

9.
Improving charge transport and reducing bulk/surface recombination can increase the activity and stability of BiVO4 for water oxidation. Herein we demonstrate that the photoelectrochemical (PEC) performance of BiVO4 can be significantly improved by potentiostatic photopolarization. The resulting cocatalyst-free BiVO4 photoanode exhibited a record-high photocurrent of 4.60 mA cm−2 at 1.23 VRHE with an outstanding onset potential of 0.23 VRHE in borate buffer without a sacrificial agent under AM 1.5G illumination. The most striking characteristic was a strong “self-healing” property of the photoanode, with photostability observed over 100 h under intermittent testing. The synergistic effects of the generated oxygen vacancies and the passivated surface states at the semiconductor–electrolyte interface as a result of potentiostatic photopolarization reduced the substantial carrier recombination and enhanced the water oxidation kinetics, further inhibiting photocorrosion.  相似文献   

10.
The reactions of platinum(II) iodide with triethyl‐ or trimethylsulfonium iodide in acetonitrile solution lead to the formation of crystalline products (Et3S)2[PtI6] ( 1 ) and [Me3S]2[PtI6]·CH3CN ( 2 ), respectively. The formation of Pt(IV) complexes may be explained either by disproportionation of PtI2 or oxidation by oxygen. Palladium(II) iodide reacts with triethylsulfonium iodide to give the palladium(II) complex (Et3S)2[PdI4] ( 3 ). The crystal structures of 1 – 3 were determined by single‐crystal X‐ray diffraction. In the crystal structures, the compounds 2 and 3 exhibit an extensive hydrogen‐bonding network.  相似文献   

11.
近年来, 太阳能驱动的光电化学水分解作为一种高效、环保、可持续的技术, 已经引起了广泛的关注. 为了更好地使用光电化学技术将太阳能转化为化学能, 至关重要的是提高光电极材料的光吸收和光转化效率. BiVO4禁带宽度(Eg=2.4-2.5 eV)小, 具有很好的可见光响应能力, 因此BiVO4光电极材料引起了广泛关注. 但是, 当单独BiVO4作为光电阳极材料时, 电子-空穴对分离弱、载流子传输慢, 从而使BiVO4不能很好地在光电化学水分解中发挥作用. 为了缓解或解决此类限制性因素, 本课题组通过水热法合成了NiFe双氢纳米粒子, 并将其负载于BiVO4电极表面, 光电催化分解水实验表明其产氢效率得到大幅度提高. 同时制备了Ni(OH)2/BiVO4和Fe(OH)2/BiVO4电极并用于研究NiFe/BiVO4电极的反应机理. 在上文基础上, 本文采用电子扫描电镜(SEM)、高分辨投射电镜(HRTEM)、X射线衍射(XRD)、紫外可见漫反射(UV-Vis DRS)等表征手段和线性扫描伏安法(LSV)和电流时间(I-t)等对其光电化学活性进行了测试, 研究了NiFe/BiVO4电极在发生水氧化时的反应机理. SEM结果表明, Ni(OH)2是以纳米片组成的纳米球负载于多孔BiVO4表面; 而当Fe(OH)2负载于BiVO4表面时, BiVO4的纳米尺寸减小; NiFe-LDH纳米粒子负载于BiVO4表面时, 可以明显看见BiVO4纳米颗粒表面包裹着一层更小的纳米粒子.这证明了Ni(OH)2, Fe(OH)2和NiFe-LDH纳米粒子均成功负载于BiVO4表面. 这也得到HRTEM结果的确认. UV-Vis DRS结果表明NiFe-LDH纳米粒子能有效拓宽BiVO4的吸收边, 从而增加对可见光的吸收, 增加了对光的利用率. LSV测试结果表明, 暗反应条件下Ni(OH)2/BiVO4比NiFe/BiVO4和Fe(OH)2/BiVO4电极的起始电位更低, 说明Ni(OH)2有更好的传输电子性能; 而在光照条件下, 在同一电位时NiFe/BiVO4比Ni(OH)2/BiVO4和Fe(OH)2/BiVO4电极的光电流值更高. 值得注意的是, 此时Ni(OH)2/BiVO4比Fe(OH)2/BiVO4电极的光电流值低, 这又说明Fe(OH)2比Ni(OH)2对光更敏感. 因此当NiFe-LDH纳米粒子负载于BiVO4表面时, 不仅提高了BiVO4光电极的光吸收效率, 而且加速了载流子的传输从而抑制了光生电子-空穴的复合, 使反应过程中的量子效率得到提高.  相似文献   

12.
Using an organic p/n bilayer comprised of 3,4,9,10-perylenetetracarboxyl-bisbenzimidazole (PTCBI, an n-type semiconductor) and 29H,31H-phthalocyanine (H2Pc, a p-type semiconductor) as a photoanode in the presence of FeII(CN)64? (an electron donor), the oxidation kinetics on the H2Pc surface was investigated with respect to the pHs employed (i.e. pH = 4, 7, and 10). The kinetic analysis of the rate-limiting charge transfer between H2Pc and FeII(CN)64? was conducted by assuming the Langmuir adsorption equilibrium at the H2Pc/water interface. In addition to a demonstration of the PTCBI/H2Pc photoanode under the weakly acidic–alkaline conditions, the present work evidently shows that the photoanodic reaction is kinetically independent of the pH conditions employed.  相似文献   

13.
Nanotubular Fe2O3 is a promising photoanode material, and producing morphologies that withstand high‐temperature calcination (HTC) is urgently needed to enhance the photoelectrochemical (PEC) performance. This work describes the design and fabrication of Fe2O3 nanotube arrays that survive HTC for the first time. By introducing a ZrO2 shell on hydrothermal FeOOH nanorods by atomic layer deposition, subsequent high‐temperature solid‐state reaction converts FeOOH‐ZrO2 nanorods to ZrO2‐induced Fe2O3 nanotubes (Zr‐Fe2O3 NTs). The structural evolution of the hematite nanotubes is systematically explored. As a result of the nanostructuring and shortened charge collection distance, the nanotube photoanode shows a greatly improved PEC water oxidation activity, exhibiting a photocurrent density of 1.5 mA cm−2 at 1.23 V (vs. reversible hydrogen electrode, RHE), which is the highest among hematite nanotube photoanodes without co‐catalysts. Furthermore, a Co‐Pi decorated Zr‐Fe2O3 NT photoanode reveals an enhanced onset potential of 0.65 V (vs. RHE) and a photocurrent of 1.87 mA cm−2 (at 1.23 V vs. RHE).  相似文献   

14.
Two mononuclear ruthenium complexes [Ru(H2tcbp)(isoq)2] ( 1 ) and [Ru(H2tcbp)(pic)2] ( 2 ) (H4tcbp=4,4′,6,6′‐tetracarboxy‐2,2′‐bipyridine, isoq=isoquinoline, pic=4‐picoline) are synthesized and fully characterized. Two spare carboxyl groups on the 4,4′‐positions are introduced to enhance the solubility of 1 and 2 in water and to simultaneously allow them to tether to the electrode surface by an ester linkage. The photochemical, electrochemical, and photoelectrochemical water oxidation performance of 1 in neutral aqueous solution is investigated. Under electrochemical conditions, water oxidation is conducted on the deposited indium‐tin‐oxide anode, and a turnover number higher than 15,000 per water oxidation catalyst (WOC) 1 is obtained during 10 h of electrolysis under 1.42 V vs. NHE, corresponding to a turnover frequency of 0.41 s?1. The low overpotential (0.17 V) of electrochemical water oxidation for 1 in the homogeneous solution enables water oxidation under visible light by using [Ru(bpy)3]2+ ( P1 ) (bpy=2,2′‐bipyridine) or [Ru(bpy)2(4,4′‐(COOEt)2‐bpy)]2+ ( P2 ) as a photosensitizer. In a three‐component system containing 1 or 2 as a light‐driven WOC, P1 or P2 as a photosensitizer, and Na2S2O8 or [CoCl(NH3)5]Cl2 as a sacrificial electron acceptor, a high turnover frequency of 0.81 s?1 and a turnover number of up to 600 for 1 under different catalytic conditions are achieved. In a photoelectrochemical system, the WOC 1 and photosensitizer are immobilized together on the photoanode. The electrons efficiently transfer from the WOC to the photogenerated oxidizing photosensitizer, and a high photocurrent density of 85 μA cm?2 is obtained by applying 0.3 V bias vs. NHE.  相似文献   

15.
Realizing nitrogen reduction reaction(NRR) to synthesis NH_3 under mild conditions has gained extensive attention as a promising alternative way to the energy-and emission-intensive Haber-Bosch process.Among varieties of potential strategies,photoelectrochemical(PEC) NRR exhibits many advantages including utilization of solar energy,water(H_2O) as the hydrogen source and ambient operation conditions.Herein,we have designed a solar-driven PEC-NRR system integrating high-efficiency Fe_2O_3-based photoanode and atomically dispersed cobalt(Co) cathode for ambient NH_3 synthesis.Using such solar-driven PEC-NRR system,high-efficiency Fe_2O_3-based photoanode is responsible for H_2O/OH oxidatio n,and meanwhile the generated photoelectrons transfer to the single-atom Co cathode for the N_2 reduction to NH_3.As a result,this system can afford an NH_3 yield rate of 1021.5 μg mgco~(-1) h~(-1) and a faradic efficiency of 11.9% at an applied potential bias of 1.2 V(versus reversible hydrogen electrode) on photoanode in 0.2 mol/L NaOH electrolyte under simulated sunlight irradiation.  相似文献   

16.
Alleviating charge recombination at the electrode/electrolyte interface by introducing an overlayer is considered an efficient approach to improve photoelectrochemical (PEC) water oxidation. A WO3 overlayer with dual oxygen and tungsten vacancies was prepared by using a solution‐based reducing agent, LEDA (lithium dissolved in ethylenediamine), which improved the PEC performance of the mesoporous WO3 photoanode dramatically. In comparison to the pristine samples, the interconnected WO3 nanoparticles surrounded by a 2–2.5 nm thick overlayer exhibited a photocurrent density approximately 2.4 times higher and a marked cathodic shift of the onset potential, which is mainly attributed to the facilitative effect on interface charge transfer and the improved conductivity by enhanced charge carrier density. This simple and effective strategy may provide a new path to improve the PEC performance of other photoanodes.  相似文献   

17.
On Pentaiodoplatinates(II, IV) M2PtI5 · 2 H2O (M ? K, Rb, NH4). Mixed-valence Compounds with Linear Chain Iodobridged Anions Pentaiodoplatinates M2PtI5 · 2 H2O (M ? K, Rb, NH4) are obtainable by crystallization from aqueous solutions formed by dissolving of tetrachloroplatinates(II) in highly concentrated solutions of alkali iodides MI. The structural parameters were determinated from single crystal data. The compounds are classed with the group of linear chain mixed-valence platinum complexes from Wolffram's Salt type. In the crystal structures PtI4-units are connected by asymnetric I-bridges to [PtI4I2/2] chains. There was no evidence of the existence of crystalline tetraiodoplatinates(II) M2PtI4.  相似文献   

18.
Sluggish oxygen evolution kinetics are one of the key limitations of bismuth vanadate (BiVO4) photoanodes for efficient photoelectrochemical (PEC) water splitting. To address this issue, we report a vanadium oxide (VOx) with enriched oxygen vacancies conformally grown on BiVO4 photoanodes by a simple photo-assisted electrodeposition process. The optimized BiVO4/VOx photoanode exhibits a photocurrent density of 6.29 mA cm−2 at 1.23 V versus the reversible hydrogen electrode under AM 1.5 G illumination, which is ca. 385 % as high as that of its pristine counterpart. A high charge-transfer efficiency of 96 % is achieved and stable PEC water splitting is realized, with a photocurrent retention rate of 88.3 % upon 40 h of testing. The excellent PEC performance is attributed to the presence of oxygen vacancies in VOx that forms undercoordinated sites, which strengthen the adsorption of water molecules onto the active sites and promote charge transfer during the oxygen evolution reaction. This work demonstrates the potential of vanadium-based catalysts for PEC water oxidation.  相似文献   

19.
The activity of WO3 photoanode could be improved efficiently after loading MnOx by photodeposition. The maximum photocurrent density of composite photoanode is achieved with a deposition time of 3 min, which is higher than that of pristine WO3 photoanode around 40%.  相似文献   

20.
使用溶胶-凝胶法制备了α-Fe2O3薄膜,研究了氢氟酸腐蚀薄膜表面对其光电化学性质的影响. 实验发现,薄膜表面的孔洞和间隙随着氢氟酸浸蚀时间的增长而发生变化. 氢氟酸浸蚀5 min,α-Fe2O3电极的光电流降低;随后随浸蚀时间增加而迅速增加;当浸蚀时间大于15 min时,其光电流再次下降,但对浸蚀过的样品再次退火可以使光电流大幅增加. 通过电化学交流阻抗谱、拉曼和X射线光电子能谱分析,提出了两个影响光电流的因素:氢氟酸表面浸蚀造成薄膜表面的多孔性和结晶度降低. 为此,通过示意图解释了结合浸蚀和退火后处理两个步骤来增强α-Fe2O3薄膜光解水电极光电活性的原理. 相对于初始的α-Fe2O3电极,浸蚀并且再退火处理后,其光电性质更加稳定.  相似文献   

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