Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

Yang, Yang; Xu, Di; Wu, Qiuxuan; Diao, Peng

doi:10.1038/srep35158

Cited by 405 publications

(374 citation statements)

References 78 publications

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“…Hydrogen generation via water splitting under sunlight on the surface of semiconductor photoelectrodes is one of the most promising way because it lets to produce fuel with the minimal environmental impact [3,4]. Photo-electrochemical water splitting process often carries out in photo-electrochemical cells (PEC) which in most cases consist of three electrodes: working (semiconductor), counter (more often is platinum), and reference (silver chloride, saturated calomel etc) electrodes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of copper oxides films via anodic oxidation of copper foil followed by thermal reduction

Zimbovskiy

Gavrilov

Чурагулов

2018

IOP Conf. Ser.: Mater. Sci. Eng.

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Abstract.Copper oxides films were successfully synthesized via anodic oxidation of copper foil at various conditions followed by thermal reduction of oxidized samples in inert nitrogen atmosphere. The morphology and phase composition of final and intermediate products were determined by scanning electron microscopy, X-ray diffraction and Raman spectroscopy techniques. Optimal synthetic conditions of Cu 2 O films on copper foil surface were established.

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Section: Introductionmentioning

confidence: 99%

Synthesis of copper oxides films via anodic oxidation of copper foil followed by thermal reduction

Zimbovskiy

Gavrilov

Чурагулов

2018

IOP Conf. Ser.: Mater. Sci. Eng.

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“…Cu 2 O thin films are attracting increasing attention as solar-cell materials, [1][2][3][4][5] photocathodes, [6][7][8][9] and photocatalysts [10][11][12] for, for example, water splitting. Among thin-film fabrication methods, electrodeposition from an aqueous solution has advantages over conventional methods, such as chemical vapor deposition, because of its low cost and low environmental burden.…”

mentioning

confidence: 99%

Identification of Copper(II)–Lactate Complexes in Cu₂O Electrodeposition Baths: Deprotonation of the α-Hydroxyl Group in Highly Concentrated Alkaline Solution

Chen

Kitada

Seki

et al. 2018

J. Electrochem. Soc.

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Unveiling dissolved species in electrodeposition baths helps our understanding of electrodeposition behavior, such as growth orientation. A highly concentrated aqueous alkaline copper(II)-lactate solution is used for the electrodeposition of copper(I) oxide (Cu 2 O) thin films with <111> orientations; the semiconductor properties of these films facilitate their use in solar-cell materials, photocathodes, and photocatalysts. However, the dissolved species, presumably copper(II)-lactate complexes, cannot be deduced on the basis of known thermodynamic data, and have not been convincingly determined yet. In this work, we determine these cupric complexes by pH titration, ultraviolet-visible spectroscopy, and electrospray-ionization mass spectrometry (ESI-MS), including probe-ESI-MS (PESI-MS). Using PESI-MS, we successfully analyzed a highly concentrated solution without sample dilution. The determined complexes are Cu(H -1 L)L -and Cu(H -1 L) 2 2-, where the H -1 L 2-(CH 3 CH(O -)COO -) is a lactate ion with a deprotonated α-hydroxyl group. As far as we know, this is the first direct experimental observation of H -1 L 2-ions in a highly concentrated aqueous alkaline copper(II)-lactate solution. We also propose that H -1 L 2-is stabilized by the high concentration and through coordination to copper(II) ions. Cuprous oxide (Cu 2 O) is a p-type semiconductor that is inexpensive and of low toxicity. Cu 2 O thin films are attracting increasing attention as solar-cell materials, 1-5 photocathodes, 6-9 and photocatalysts 10-12 for, for example, water splitting. Among thin-film fabrication methods, electrodeposition from an aqueous solution has advantages over conventional methods, such as chemical vapor deposition, because of its low cost and low environmental burden. Moreover, it is easy to obtain cubic Cu 2 O with the preferential <111> orientation by tuning the pH of the electrodeposition bath;13-17 this orientation relaxes lattice misfit with hexagonal ZnO, which is favorable for Cu 2 O-ZnO solar cells.Since the pioneering work of Rakhshani et al., 13 highly concentrated aqueous alkaline solutions have commonly been used for Cu 2 O electrodeposition;13-16 these solutions contain 0.4 M of a copper(II) salt and 3.0 M lactic acid (HL; CH 3 CH(OH)COOH) as the complexing agent, and the pH is adjusted to be in the 9.0-12.5 range. [13][14][15][16] The crystal orientation of the electrodeposited Cu 2 O is pH dependent; i.e. it is <100> at pH values of 9.0 and 9.5, and <111> at pH values of 12.0 and 12.5. [13][14][15][16][17] The pH dependence of the crystal orientation during Cu 2 O electrodeposition may be ascribable to changes in the dissolved copper(II)-lactate complexes. 6,15,16 Unfortunately, to the best of our knowledge, there are no available thermodynamic data for these copper(II)-lactate complexes under these alkaline conditions, especially for such concentrated solutions. Two previous reports have indicated the presence of dissolved copper(II)-lactate complexes in such concentrated alkaline solutions; Leopold et al. a...

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“…The XRD pattern of Cu 2+ ions coordinated Ti‐MOF reveals that the sample has a slight amorphous character, which is supported with the data obtained from TEM for the same samples. This can be ascribed to the formation of CuO x oxides in the Ti‐MOF . In addition, the formation of CuO x along with Cu 2+ coordination might also facilitate an improved optical absorption of Cu‐MOF.…”

Section: Resultsmentioning

confidence: 99%

Amine Functionalized Metal–Organic Framework Coordinated with Transition Metal Ions: d–d Transition Enhanced Optical Absorption and Role of Transition Metal Sites on Solar Light Driven H₂ Production

Karthik

Neppolian

Vinu

et al. 2019

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Design and development of efficient photocatalysts for H2 production from water and sunlight have gained significant attention as the solar assisted approach is considered to be a promising approach for the generation of clean fuel. However, the poor charge carrier separation and light harvesting ability of existing photocatalysts limits the efficiency of photoconversion of water. In this work, the synthesis of transition metal ions (M2+ = Co2+, Cu2+, and Ni2+) coordinated with Ti‐metal organic frameworks (Ti‐MOFs) through a simple post‐synthetic coordination method for efficient solar light‐driven H2 production is reported. Notably, coordination of M2+ ions with Ti‐MOF significantly improves the optical absorption by d–d transitions and the multimetal sites facilitate the fast charge carrier separation, thereby enhancing the solar light‐driven H2 production activity. Very interestingly, the rate of solar light‐driven H2 production is varied with respect to different metal ions coordination due to the position of d–d bands absorption in the solar spectrum, and the complexing tendency of M2+ ions with sacrificial electron donors. A maximum solar H2 production rate of 1583.55 µmol h−1 g−1 is achieved with a Cu2+ coordinated Ti‐MOF, which is ≈13 fold higher than that of the pristine Ti‐MOF.

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Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

Cited by 405 publications

References 78 publications

Synthesis of copper oxides films via anodic oxidation of copper foil followed by thermal reduction

Synthesis of copper oxides films via anodic oxidation of copper foil followed by thermal reduction

Identification of Copper(II)–Lactate Complexes in Cu₂O Electrodeposition Baths: Deprotonation of the α-Hydroxyl Group in Highly Concentrated Alkaline Solution

Amine Functionalized Metal–Organic Framework Coordinated with Transition Metal Ions: d–d Transition Enhanced Optical Absorption and Role of Transition Metal Sites on Solar Light Driven H₂ Production

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Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

Cited by 405 publications

References 78 publications

Synthesis of copper oxides films via anodic oxidation of copper foil followed by thermal reduction

Synthesis of copper oxides films via anodic oxidation of copper foil followed by thermal reduction

Identification of Copper(II)–Lactate Complexes in Cu2O Electrodeposition Baths: Deprotonation of the α-Hydroxyl Group in Highly Concentrated Alkaline Solution

Amine Functionalized Metal–Organic Framework Coordinated with Transition Metal Ions: d–d Transition Enhanced Optical Absorption and Role of Transition Metal Sites on Solar Light Driven H2 Production

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Identification of Copper(II)–Lactate Complexes in Cu₂O Electrodeposition Baths: Deprotonation of the α-Hydroxyl Group in Highly Concentrated Alkaline Solution

Amine Functionalized Metal–Organic Framework Coordinated with Transition Metal Ions: d–d Transition Enhanced Optical Absorption and Role of Transition Metal Sites on Solar Light Driven H₂ Production