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1.
Uniform flower-like TiO_2 coated Au nanostars and core-shell Au@Ag natiostars with different amounts of Ag coating were prepared through a facile method by hydrolysis of TiF_4 under an acidic environment.The photocatalytic capability of these flower-like nanocomposites under visible light irradiation was found to be enhanced by up to 4.7-fold compared to commercial P25 TiO_2 nanoparticles.The enhanced photocatalytic activity was ascribed to improved light absorption and hot electron injection from the photo-excited Au@Ag core to the TiO_2 shell.  相似文献   

2.
PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C3N4) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H2 evolution of the g-C3N4 nanosheets shows that it was significantly enhanced when PtPd alloy NPs were introduced as a co-catalyst. The 0.2 wt% PtPd/g-C3N4 composite photocatalyst gave a maximum H2 production rate of 1600.8 μmol g–1 h–1. Furthermore, when K2HPO4 was added to the reaction system, the H2 production rate increased to 2885.0 μmol g–1 h–1. The PtPd/g-C3N4 photocatalyst showed satisfactory photocatalytic stability and was able to maintain most of its photocatalytic activity after four experimental photocatalytic cycles. In addition, a possible mechanism for the enhanced photocatalytic activity was proposed and verified by various photoelectric techniques. These results demonstrate that the synergistic effect between PtPd and g-C3N4 helps to greatly improve the photocatalytic activity of the composite photocatalyst.  相似文献   

3.
Graphitic carbon nitride (g‐C3N4)‐based photocatalysts have received considerable attention in the field of photocatalysis, especially for photocatalytic H2 evolution. However, the intrinsic disadvantages of g‐C3N4 seriously limit its practical application. Herein, CdS nanospheres with an average diameter of 135 nm prepared using a solvothermal method were used as co‐catalysts to form CdS/g‐C3N4 composites (CSCN) to enhance the photocatalytic activity. Various techniques were employed to characterize the structure, composition and optical properties of the as‐prepared samples. It was found that the CdS nanospheres were relatively uniformly dispersed on the surface of g‐C3N4. Moreover, the photocatalytic H2 generation activity of the samples was evaluated using lactic acid as sacrificial reagent in water under visible light irradiation. When the amount of CdS nanospheres loaded in the hybridized composites was 5 wt%, the optimal H2 evolution rate reached 924 μmol g?1 h?1, which was approximately 1.4 times higher than that (680 μmol g?1 h?1) of Pt/g‐C3N4 (3 wt%). Based on the results of analysis, a possible mechanism for the photocatalytic activity of CSCN is proposed tentatively.  相似文献   

4.
全球工业化进程的加快使人们饱受环境污染问题的困扰.半导体光催化技术作为一种高效、绿色、有潜力的新技术,在环境净化方面有着广阔的应用前景.Bi2O4是近年来新开发出的一种铋基光催化剂,在环境净化方面已有一些研究.但是,单体光催化剂通常存在光响应范围窄、光生载流子复合率高等问题,这些不足限制了Bi2O4的进一步应用.因此,需要通过适当的改性来拓宽其光响应范围和提高其载流子的分离效率,从而提高其光催化活性.构建Z型异质结被认为是提高光催化剂光生载流子分离效率并进一步提高光催化活性的有效方法.MoO3是一种宽禁带的n型半导体,具有独特的能带结构、光学特性和表面效应,是一种非常有前景的半导体光催化剂.虽然MoO3材料的光生载流子复合率高,带隙(2.7-3.2 eV)大,不利于其参与光催化反应,但MoO3与其他合适的半导体配位形成复合材料后能够有效提高其光生载流子的分离效率,从而提高其光催化活性.本研究采用简单的水热法制备了一种新型Z型MoO3/Bi2O4复合光催化剂,SEM和TEM分析结果表明,MoO3和Bi2O4紧密结合在一起.X射线光电子能谱分析表明,MoO3和Bi2O4之间存在很强的界面相互作用,这有助于电荷转移和光生载流子的分离.光致发光光谱、电阻抗和光电流测试也证明了MoO3/Bi2O4复合光催化剂的光生载流子分离效率更高,形成了更强的光电流.通过在可见光下降解RhB溶液评价了所合成光催化剂的光催化性能.15%MoO3/Bi2O4(15-MB)复合光催化剂表现出了最佳的可见光催化活性,在40 min内对10 mg/L RhB溶液的降解率达到了99.6%,其降解速率是Bi2O4的2倍.此外,15-MB复合光催化剂在经过五次循环降解RhB溶液后仍保持良好的光催化活性和稳定性,表明MoO3/Bi2O4复合光催化剂具有较强的应用潜力.通过自由基捕获实验确定了光催化反应中主要的活性自由基为 O2-和h+.通过莫特-肖特基测试和带隙计算得到MoO3和Bi2O4的价带和导带位置.最后,根据实验和分析结果提出了Z型MoO3/Bi2O4复合光催化剂在可见光下降解RhB溶液的机理.本研究为设计铋基Z型异质结光催化剂用于高效去除环境污染物提供了一种有前景的策略.  相似文献   

5.
Polypyrrole-modified graphitic carbon nitride composites (PPy/g-C3N4) are fabricated using an in-situ polymerization method to improve the visible light photocatalytic activity of g-C3N4. The PPy/g-C3N4 is applied to the photocatalytic degradation of methylene blue (MB) under visible light irradiation. Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as-prepared composites. Results show that the specific surface area of the PPy/g-C3N4 composites increases upon assembly of the amorphous PPy nanoparticles on the g-C3N4 surface. Owing to the strong conductivity, the PPy can be used as a transition channel for electrons to move onto the g-C3N4 surface, thus inhibiting the recombination of photogenerated carriers of g-C3N4 and improving the photocatalytic performance. The elevated light adsorption of PPy/g-C3N4 composites is attributed to the strong absorption coefficient of PPy. The composite containing 0.75 wt% PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g-C3N4 in 2 h. Moreover, the degradation kinetics follow a pseudo-first-order model. A detailed photocatalytic mechanism is proposed with ·OH and ·O2? radicals as the main reactive species. The present work provides new insights into the mechanistic understanding of PPy in PPy/g-C3N4 composites for environmental applications.  相似文献   

6.
Uniform flower-like TiO2 coated Au nanostars and core-shell Au@Ag nanostars with different amounts of Ag coating were prepared through a facile method by hydrolysis of TiF4 under an acidic environment. The photocatalytic capability of these flower-like nanocomposites under visible light irradiation was found to be enhanced by up to 4.7-fold compared to commercial P25 TiO2 nanoparticles. The enhanced photocatalytic activity was ascribed to improved light absorption and hot electron injection from the photo-excited Au@Ag core to the TiO2 shell.  相似文献   

7.
Y(2)Ta(2)O(5)N(2) is presented as a novel photocatalyst with high activity for water splitting under visible-light irradiation in the presence of appropriate sacrificial reagents; the activity for reduction to H(2) is increased by the incorporation of Pt or Ru as a co-catalyst, with a significant increase in production efficiency when both Pt and Ru are present.  相似文献   

8.
In the present study, Nd3+-doped ZnSe nanoparticles with variable Nd contents were successfully synthesized via a hydrothermal process using Neodymium (III) chloride hexahydrate as the doping source. X-ray diffraction, UV–Vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy and transmission electron microscopy were used for characterization of the synthesized nanoparticles. It was confirmed by the DRS analysis that both of the undoped and Nd-doped ZnSe samples had significant optical absorption in the visible light range. The photocatalytic performance of as-synthesized nanoparticles was investigated towards the decolorization of C. I. Acid Orange 7 solution under visible light irradiation. Results indicated that the loading of Nd dopant into ZnSe nanoparticles significantly enhanced the photocatalytic activity of pure ZnSe with increasing Nd loading up to 6 mol% (color removal efficiency of 24.31 % for ZnSe and 84.20 % for Nd0.06Zn0.94Se after 120 min of treatment) and then the photocatalytic activity began to decrease.  相似文献   

9.
Aurivillius structure Bi(2)MoO(6) (BG: 2.70 eV) that is a low-temperature phase showed an intense absorption band in the visible light region and photocatalytic activity for O(2) evolution from an aqueous silver nitrate solution under visible light irradiation, among various bismuth molybdates (Bi(2)MoO(6), Bi(2)Mo(2)O(9), and Bi(2)Mo(3)O(12)) synthesized by solid-state and reflux reactions. Bi(2)Mo(3)O(12) (BG: 2.88 eV) also showed photocatalytic activity for O(2) evolution under full-arc irradiation of a Xe lamp (lambda > 300 nm). The photocatalytic activity of the Aurivillius structure Bi(2)MoO(6) prepared by the reflux method was dependent on the annealing temperature after the preparation. The crystallinity was the important factor for the activity. Calculation by the density functional method indicated that the conduction band of Aurivillius structure Bi(2)MoO(6) was made up of Mo 4d orbitals. It turned out that the visible-light absorption of this photocatalyst was due to the transition from the valence band consisting of O 2p orbitals to the conduction band. The corner-sharing structure of the MoO(6) octahedra contributed to the visible light response and the photocatalytic performance because excitation energy and/or photogenerated electron and hole pairs began to migrate easily in the Aurivillius structure.  相似文献   

10.
法文君  王平  岳冰  杨风岭  李大鹏  郑直 《催化学报》2015,(12):2186-2193
半导体光催化氧化技术作为一种“绿色技术”,被广泛应用于环境污染物治理和太阳能转化领域.高效、稳定、可回收利用的催化剂的开发是光催化技术发展的一个重要方向. Ag系半导体光催化剂因在可见光分解水制氢及降解有机污染物等方面表现出优异的催化性能而广受关注.然而,该催化剂失活快制约了其应用.因此,提高Ag系半导体材料的光催化稳定性成为近年来研究的一个热点.研究发现,在半导体的表面或者界面形成p–n异质结是提高催化剂光催化性能和稳定性的有效途径.理论上讲,当p型半导体和n型半导体形成p–n结以后,在两种半导体接触边缘的附近处存在着正、负空间电荷分列两边的偶极层,产生了从n型半导体指向p型半导体的内建电场.内建电场的存在使得p型半导体与n型半导体之间产生了电位差,即内建电势差.这种电势差能够有效促进电子和空穴的分离,达到光生电子和空穴对分离、转移和传递的目的,从而抑制电子和空穴的复合,提高光催化效率. Ag2CO3是p型半导体,其导带为0.21 eV,价带为2.83 eV; Ag3PO4是n型半导体,其导带为0.43 eV,价带为2.86 eV.两者能带结构匹配,能形成p–n异质结.因此,本文采用简单的共沉淀法,制备了不同比例的Ag3PO4/Ag2CO3复合光催化剂,并通过X射线衍射、透射电镜、X射线光电子能谱、紫外-可见漫反射光谱以及瞬态光电压谱等对其进行了表征.透射电镜照片显示,粒径较小的Ag3PO4颗粒均匀的分布在粒径较大的Ag2CO3周围. P元素和C元素的摩尔比接近于投料比. Ag3PO4/Ag2CO3复合催化剂的吸收光谱体现出两种催化剂的混合特征,在可见光区的吸收强度增加.瞬态光电压表征不仅证实了Ag2CO3是p型半导体, Ag3PO4是n型半导体,更说明了40%-Ag3PO4/Ag2CO3复合光催化剂的载流子寿命较长.罗丹明B(RhB)的降解实验证实40%-Ag3PO4/Ag2CO3(Ag3PO4与Ag2CO3的摩尔比为40%:60%)复合催化剂的光催化效率最高,500 W氙灯(附加420 nm截止波长的滤光片)照射15 min后, RhB就能被完全降解,而纯的Ag3PO4和Ag2CO3对RhB的降解率只有40%和10%.循环实验发现,前两次循环中由于单质银的生成导致催化剂活性下降,但从第三次循环开始其催化活性趋于稳定.此外,还通过添加草酸钠(空穴的清除剂)、异丙醇(羟基自由基的清除剂)和对苯醌(超氧自由基的淬灭剂)等来判断光催化过程中起主要作用的活性自由基.实验证实空穴是Ag3PO4/Ag2CO3光催化剂在降解RhB过程中产生的主要活性自由基物种. Ag3PO4/Ag2CO3光催化剂相对于单纯的Ag3PO4和Ag2CO3有更高的空穴产生能力.当可见光照射到复合催化剂表面时, Ag2CO3导带上的激发电子能够快速转移到Ag3PO4的导带上,同时Ag3PO4价带上的光生空穴能够快速转移到Ag2CO3的价带上. p–n结的形成提高了光生电子和空穴的分离效率,抑制了电子和空穴的再结合,因此,复合光催化剂光催化降解效率提高.综上所述, Ag3PO4/Ag2CO3之间能形成有效p–n结,40%-Ag3PO4/Ag2CO3复合光催化剂表现出最佳的光催化性能.  相似文献   

11.
半导体光催化技术因其能够完全矿化和降解废水以及废气中的各种有机和无机污染物而受到越来越多研究者关注.尽管TiO2作为光催化剂显示了良好的应用前景,但其只对紫外光响应,该部分能量大约仅占太阳光谱的5%,从而限制了其实际应用.因此,开发新型可见光响应光催化剂成为光催化领域的研究焦点之一.石墨相氮化碳(g-C3N4)作为一种光催化材料,由于具有良好的热和化学稳定性以及可见光响应而备受关注.然而,单纯的g-C3N4由于光生电荷载流子易复合,光催化效果并不理想.为进一步提高g-C3N4的光催化活性,构建g-C3N4基异质结复合光催化材料被认为是增强g-C3N4光生电子-空穴分离效率的有效方法.CdMoO4作为一种光催化材料,与g-C3N4匹配的能带有利于光生电子-空穴的分离,从而提高g-C3N4的光催化活性.本文通过便利的原位沉淀-煅烧过程,制备了新颖的CdMoO4/g-C3N4异质复合光催化材料.复合材料的晶相构成、形貌、表面化学组分和光学特性等通过相应的分析测试手段进行表征.光催化活性通过可见光下催化降解罗丹明B水溶液来评价.结果显示,将CdMoO4沉积在g-C3N4表面形成复合材料可明显提高光催化活性,且当CdMoO4含量为4.8 wt%时达到最佳的光催化活性.这种显著增强的光催化活性可能是由于CdMoO4/g-C3N4复合物能够有效地传输和分离光生电荷载流子,从而抑制了光生电子-空穴的复合.电化学阻抗、瞬态光电流和稳定荧光光谱测试结果证实,通过CdMoO4与g-C3N4复合可有效增强电荷分离效率.此外,活性物捕获实验表明,在光催化过程中空穴(h+)和超氧自由基(?O2?)是主要活性物种.根据莫托-肖特基实验并结合紫外-可见漫反射吸收光谱,得到了单纯g-C3N4和CdMoO4的能带结构,提出了形成的II型异质结有助于增强光催化活性的机理.  相似文献   

12.
Herein, cobalt (Co)-based metal–organic zeolitic imidazole frameworks (ZIF-67) coupled with g-C3N4 nanosheets synthesized via a simple microwave irradiation method. SEM, TEM and HR-TEM results showed that ZIF-67 were uniformly dispersed on g-C3N4 surfaces and had a rhombic dodecahedron shape. The photocatalytic properties of g-C3N4/ZIF-67 nanocomposite were evaluated by photocatalytic dye degradation of crystal violet (CV), 4-chlorophenol (4-CP) and photocatalytic hydrogen (H2) production. In presence of visible light illumination, the photocatalytic dye results showed that 95% CV degradation and 53% 4-CP degradation within 80 min. The H2 production of the g-C3N4/ZIF-67 composite was 2084 μmol g−1, which is 3.84 folds greater than that of bare g-C3N4 (541 μmol g−1).  相似文献   

13.
NaTaO_(3-x)N_x catalysts were synthesized by a hydrothermal(H) and a solid-state(S) methods in this study.The H-and S-NaTaO_(3-x)N_x samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), UV–visible(UV–vis) diffuse reflectance spectroscopy, and photoluminescence(PL) spectroscopy. The XRD patterns of the H-and S-samples showed peaks indexed to the pure phase of perovskite NaTaO_3 and minor peaks assignable to Ta_3N_5 at various synthesis temperatures. Substitution of oxygen by nitrogen ions causes the light absorption of the H-and S-NaTaO_(3-x)N_x samples to be extended to the 600–650 nm region, thus making the samples visible-light active. The NaTaO_(3-x)N_x samples exhibited photocatalytic activity for H_2 and O_2 evolution from aqueous methanol and silver nitrate solutions under visible-light irradiation. The UV–vis and PL spectra of the Hand S-catalysts revealed the presence of cationic vacancies and reduced metallic species, which acted as recombination centers. These results demonstrated that the preparation method plays a critical role in the formation of defect states, thereby governing the photocatalytic activity of the NaTaO_(3-x)N_x catalysts.  相似文献   

14.
一维La(OH)3纳米棒具有特殊的电子结构和多功能特性,特别是作为半导体光催化剂引起了人们极大的兴趣.但La(OH)3禁带宽度较大,且只能吸收紫外光,所以光催化效率较低,可见光利用能力较差,限制了La(OH)3的实际应用.因此,需要开发一种高效的改进方法来提高La(OH)3的可见光催化性能.本课题组发展了一种有效的改进La(OH)3方法,通过简易的方法将BiOI纳米颗粒沉积在La(OH)3纳米棒上,有效增强了对可见光的吸收能力和光生载流子的分离能力.本文采用X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)、荧光光谱(PL)、光电子能谱(XPS)、电子自旋共振(ESR)、N2吸附和元素分析等手段研究了BiOI@La(OH)3纳米棒异质结的构建原理及增强可见光催化性能的原因.XRD和XPS结果表明,通过简易化学沉积法原位构建了BiOI@La(OH)3异质结,并且在异质结中没有杂相生成.由SEM图像可见,原始La(OH)3由分散的一维纳米棒组成,平均直径为30–50 nm.通过BiOI与La(OH)3表面的紧密接触成功构建异质结,但BiOI纳米颗粒未改变La(OH)3纳米棒的形貌.由TEM和HRTEM图像可见,La(OH)3纳米棒的平均长度为30–50 nm,并且在BiOI@La(OH)3异质结中可以清晰看出BiOI和La(OH)3之间紧密接触的界面和晶格间距.N2物理吸附结果显示,随着BiOI量的增加,BiOI@La(OH)3异质结的比表面积增加,但孔体积未现明显变化.UV-Vis DRS结果显示,引入BiOI后明显促进了La(OH)3对可见光的吸收能力和利用效率,从而有利于增强可见光催化活性.通过理论计算分别得到BiOI和La(OH)3的价带和导带位置,表明具有非常匹配的能带结构可以促进BiOI光生电子的有效转移.可见光催化去除NO测试结果表明,BiOI@La(OH)3异质结的光催化活性高达50.5%,明显优于BiOI和La(OH)3.ESR测试结果显示,BiOI@La(OH)3异质结可见光催化活性中起主要作用的活性物种是?OH.结合表征结果,BiOI@La(OH)3纳米棒异质结可见光催化性能增强的原因主要有三个:(1)BiOI@La(OH)3异质结增大的比表面积有利于反应物和产物在催化剂表面扩散,同时可提供更多活性位点参与光催化反应;(2)禁带宽度影响光催化效率,当BiOI与La(OH)3达到合适比例时,既可以促进可见光吸收,也可以使光生电子具有较强还原能力;(3)BiOI@La(OH)3异质结有利于光生载流子的分离,从而显著提高其光催化活性.  相似文献   

15.
《Comptes Rendus Chimie》2015,18(8):875-882
W–S–N-tri-doped TiO2 photocatalysts (WSNTiO2) were prepared by a simple sol–gel method. Tungstic acid, sodium sulfate and urea were used as tungsten, sulfur and nitrogen sources, respectively. The morphology and microstructure characteristics of the photocatalysts were evidenced by means of XRD, BET, TEM, SEM and UV–vis DRS techniques. The XRD results show that the main crystal phase of samples is anatase. It was also found that the tri-doping of TiO2 increases its BET specific surface area from 95 to 121 m2·g−1. Besides, it was shown that tri-doping narrows the band gap of TiO2 effectively, which has greatly improved the photocatalytic activity in the visible light region. The photocatalytic activity of tri-doped TiO2 powders was compared to that of bi-doped ones through the degradation of Congo Red (CR) under visible irradiation. Thus, the prepared 0.5% W–N–S–TiO2 heat treated at 450 °C showed the best photocatalytic activity compared to the prepared pure TiO2, Degussa P25, and co-doped samples (WNTiO2 and WSTiO2). In particular, a Congo Red degradation rate of approximately 99% was reached after only 35 min of visible light irradiation in the presence of 0.5% of WNSTiO2. Total organic carbon (TOC) removal of CR was up to 72% and confirmed its significant mineralization in the presence of 0.5% of WNSTiO2 photocatalyst.  相似文献   

16.
SiC-BiVO4-P and SiC-BiVO4-H composites have been prepared by precipitation method and hydrothermal method, respectively. Rod-like BiVO4 particles dispersed on the surface of micro-sized SiC particles homogeneously in SiC-BiVO4-H. Due to the formed heterostructure between BiVO4 and SiC, photo-generated electrons and holes were effectively separated. Under visible light irradiation, SiC-BiVO4-H exhibited the best performance for photocatalytic oxidation of Rhodamine B, achieved about 7.5 times improvement in photocatalytic degradation rate constants compared with that of the pristine SiC powder. The possible photocatalysis mechanism of SiC/BiVO4 related to the band positions of the semiconductors under visible light irradiation was also discussed in detail. In addition, the radicals trapping experiments revealed that all three radicals (holes, OH, and O2?) play an important role in the Rhodamine B degradation.  相似文献   

17.
Journal of Solid State Electrochemistry - Rutile TiO2 forms on TiC coatings (TiO2/TiC coatings) during carbon-embedding heat treatment (cHT) for TiC coatings. The photocatalytic activity of...  相似文献   

18.
TaON modified by polyaniline (PANI), was prepared through a facile chemisorption process. PANI-modified TaON composites with good stabilities exhibit significantly higher photocatalytic activities than that of neat TaON on degradation of RhB under visible light irradiation, which may result from an enhancement of electron-hole separation between PANI and TaON.  相似文献   

19.
Semiconducting silver iodate (AgIO(3)) was used to modify the visible light response of an AgI/TiO(2) (AIT) catalyst by a facile method. The uncalcined AIT (AITun) and AIT calcined at 200°C (AIT200) consisted of AgIO(3), AgI, and TiO(2) semiconductors, while that calcined at 450 °C (AIT450) was composed of AgI and TiO(2). The activity in p-chlorophenol (PCP) degradation under visible light irradiation using either AITun or AIT200 was much higher than that with AIT450, which was mainly attributed to the fact that the presence of AgIO(3) provided a new matching band potential. AIT200 exhibited better photocatalytic properties than AITun due to its higher crystallinity after calcination. Moreover, the high catalytic activity of AIT200 was maintained after five successive cyclic experiments under visible irradiation. Considering the effect of radical scavengers and N(2) purging on the photocatalysis process, we deduced that the probable pathway of PCP degradation was mainly a surface charge process, caused by valence band holes.  相似文献   

20.
Photocatalytic H2 production via water splitting in a noble-metal-free photocatalytic system has attracted much attention in recent years. In this study, noble-metal-free Ni3N was used as an active cocatalyst to enhance the activity of g-C3N4 for photocatalytic H2 production under visible-light irradiation (λ > 420 nm). The characterization results indicated that Ni3N nanoparticles were successfully loaded onto the g-C3N4, which accelerated the separation and transfer of photogenerated electrons and resulted in enhanced photocatalytic H2 evolution under visible-light irradiation. The hydrogen evolution rate reached ~305.4 μmol h?1 g?1, which is about three times higher than that of pristine g-C3N4, and the apparent quantum yield (AQY) was ~0.45% at λ = 420. Furthermore, the Ni3N/g-C3N4 photocatalyst showed no obvious decrease in the hydrogen production rate, even after five cycles under visible-light irradiation. Finally, a possible photocatalytic hydrogen evolution mechanism for the Ni3N/g-C3N4 system is proposed.  相似文献   

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