Highly efficient photocatalytic hydrogen evolution driven by adjustable bimetal CuNi derived hexagonal Ni(OH)2

doi:10.1016/j.apsusc.2020.146154

Applied Surface Science

Volume 524, 15 September 2020, 146154

https://doi.org/10.1016/j.apsusc.2020.146154 Get rights and content

Highlights

•
CuNi bimetal-derived Ni(OH)₂ composite catalyst is obtained by hydrothermal method.
•
Non-semiconductor driven photocatalysts are used in the field of photocatalysts.
•
The possible mechanism to improve the photocatalytic activity is clarified.

Abstract

In the field of photocatalysis, most of the photocatalysts are semiconductors. Recent years, there have been many photocatalytic systems related to non-semiconductor catalysts. In this paper, a photocatalytic hydrogen evolution system of hexagonal Ni(OH)₂ derived from CuNi bimetal is obtained by classical hydrothermal method. The derived hexagonal Ni(OH)₂ can promote the separation of photogenerated electron-hole pairs and greatly improve the effect of photocatalytic hydrogen evolution. The electron-hole pair comes from the surface plasmon resonance (SPR) effect of Cu from CuNi composite. It is worth noting that photoluminescence spectra and photoelectrochemical experiments have confirmed that the CuNi-5 complex can effectively improve space charge separation. The results of linear scanning voltammetry show that the material has high current response characteristics. This system gives a practical solution for planning and synthesizing non-semiconductor catalysts with high photocatalytic activity.

Graphical abstract

Introduction

Facing increasing environmental pollution and severe energy shortage, we need to find clean energy that can effectively solve these problems. Currently, photocatalytic hydrogen production has attracted the attention of researchers due to its environmental and economic advantages. At the same time, hydrogen has a high energy density of 143 MJ kg⁻¹ [1], [2]. Among the emerging advanced hydrogen production technologies, the photocatalytic hydrogen evolution method has many advantages such as renewable, high stability, environmental friendliness, and safety, and has far better prospects than other methods [3], [4], [5], [6]. The ideal semiconductor for photocatalytic hydrogen evolution requires a proper band gap width to expand the absorption of photons in the solar spectrum, effectively reducing the recombination of photogenerated charge carriers, and provide an abundant chemical potential during the redox reaction. However, the embedding of bimetal achieves a spectral region that effectively broadens the photoresponse and reasonably reduces the bandgap of the semiconductor [7], [8].

Generally speaking, bimetals play the role of cocatalyst in photocatalysis, and semiconductors are still the key to catalysts [9], such as g-C₃N₄/Ni(OH)₂ [10], Ni(OH)₂/CdS/TiO₂ [11], Ni(OH)₂/MoS₂ [12]. Due to their peculiar internal structure and strain effects caused by ligands, bimetals generally have better catalytic performance than single metals [13], [14]. CuNi bimetal is an important catalyst and has been reported to be used in various catalytic reactions, such as: non-enzymatic method for testing glucose [15], [16], conversion of synthetic methanol to water gas [17]. Related literature reports that the work function of Ni is 5.15 eV, and the work function of Cu is 4.65 eV [18]. In this work, the first-principles were used to count the adsorption energies of the H atoms and H₂ molecules of Cu and Ni [19]. The H atoms adsorption energies of Cu and Ni are 2.49 and 2.73 eV per H (eV per H atoms), respectively, and the corresponding H₂ molecules have adsorption energies of 0.001 and 0.102 eV per H₂ (eV per H₂) [20]. The above results indicate that Cu has good hydrogen evolution activity, but it is difficult to trap H atoms and photoelectrons. Therefore, we compensate for this defect by synthesizing the CuNi bimetal [21], [22]. To achieve the optimal co-catalytic performance by controlling the hydrogen evolution path and by properly adjusting the ratio of the CuNi bimetal. However, a photocatalytic hydrogen release system of CuNi bimetal-derived Ni(OH)₂ as a photocatalyst has not been reported so far. Compared to the precious metals Pt, Au and Se, Cu and Ni are cheaper and easier to obtain [23], [24].

According to reports, Yu and colleagues [26], [27] conducted a series of studies on Ni(OH)₂ to reduce CO₂ through various photocatalysts. It is found that Ni(OH)₂ is a very useful catalyst for photocatalytic hydrogen release during photodecomposition [25]. Inspired by the literature, we have designed a new system of CuNi bimetal derived Ni(OH)₂, in which Ni(OH)₂ acts as a water dissociation promoter and generates hydrogen. The intermediate is then adsorbed at a position above the bimetal CuNi and molecular hydrogen is generated. The experimental results show that the CuNi bimetal derived hexagonal Ni(OH)₂ has high photocatalytic hydrogen evolution performance.

Section snippets

Materials

Copper chloride dihydrate (CuCl₂·2H₂O, AR), nickel chloride hexahydrate (NiCl₂·6H₂O, AR), sodium hypophosphite (AR), purchased from Aladdin official reagent. Sodium hydroxide (NaOH, 96%) and ethylenediamine (99%) are purchased from Beijing Chemical Plant. The above materials are used without further purification.

Catalyst synthesis

The CuNi bimetal was synthesized by an one-step hydrothermal method. In preparation process, dissolved CuCl₂·2H₂O (x mmol) and NiCl₂·6H₂O (1-x mmol) in 50 ml of a certain concentration

Structures and characterizations

The Fig. 1 indicates X-ray diffraction pattern of different samples prepared. According to the standard cards Cu (PDF # 04-0386) [33], Ni (PDF # 04-0850) and Ni(OH)₂ (PDF # 14-0117), three different crystal phases are shown in Fig. 1a. The three characteristic diffraction peaks of cubic copper belong to (2 2 0), (2 0 0) and (1 1 1) crystal planes, respectively, and the three characteristic diffraction peaks of cubic nickel belong to the (2 2 0), (2 0 0) and (1 1 1) crystal planes, respectively.

Conclusion

In short, we reasonably designed a controllable CuNi bimetal-derived Ni(OH)₂, whose composition can be adjusted by changing the NaOH concentration of the synthesis reaction. More importantly, compared to the CuNi bimetal alone, under visible light irradiation, the catalyst CuNi-5 exhibits better photocatalytic water decomposition performance in the EY-sensitized system, which will undoubtedly be a better way to develop non-semiconductor catalysts multiple potential applications provide

CRediT authorship contribution statement

Lingjiao Li: Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Validation, Visualization, Writing - original draft, Writing - review & editing. Jing Xu: Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Writing - review & editing. Binyi Su: Investigation, Methodology, Validation.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was supported by the Natural Science Foundation of Ningxia Province (NZ17262) and the Graduate student innovation project of North Minzu University (YCX19112). It also was supported by the New Catalytic Process in Clean Energy Production (ZDZX201803), the Open Project of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University (2019-KF-36).

References (37)

J. Tian et al.
Carbon quantum dots/hydrogenated TiO₂ nanobelt heterostructures and their broad spectrum photocatalytic properties under UV, visible, and nearinfrared irradiation
NANO Energy
(2015)
Khurram Shahzad et al.
Engineering the performance of heterogeneous WO₃/fullerene@Ni₃B/Ni(OH)₂ Photocatalysts for Hydrogen Generation
Int. J. Hydrogen Energy
(2019)
Y. Mizukoshi et al.
Dependence of photocatalytic activities upon the structures of Au/Pd bimetallic nanoparticles immobilized on TiO₂ surface
Appl. Catal. B
(2010)
Mirabbos Hojamberdiev et al.
Synergistic effect of g-C₃N₄, Ni(OH)₂ and halloysite in nanocomposite photocatalyst on efficient photocatalytic hydrogen generation
Renewable Energy
(2019)
J.M. Wang et al.
Synergetic effect of Ni(OH)₂ cocatalyst and CNT for high hydrogen generation on CdS quantum dot sensitized TiO₂ photocatalyst
Appl. Catal. B
(2017)
Bao Zhang et al.
Interface engineering: The Ni(OH)₂/MoS₂ heterostructure for highly efficient alkaline hydrogen evolution
NANO Energy
(2017)
Y. Zhang et al.
Incorporation of RuO₂ into charcoal-derived carbon with controllable microporosity by CO₂ activation for high-performance supercapacitor
Carbon
(2017)
X. Hao et al.
Architecture of high efficient zinc vacancy mediated Z–scheme photocatalyst from metal–organic frameworks
NANO Energy
(2018)
P.Y. Zhang et al.
Plasmonic Cu nanoparticle on reduced graphene oxide nanosheet support: an efficient photocatalyst for improvement of near-infrared photocatalytic H₂ evolution
Appl. Catal. B – Environ.
(2018)
L. Lin et al.
The visible-light-assisted thermocatalytic methanation of CO₂ over Ru/TiO_(2–x)N_x
Appl. Catal. B-Environ.
(2017)

P.Y. Zhang et al.

Synthesis of a plasmonic CuNi bimetal modified with carbon quantum dots as a non-semiconductor-driven photocatalyst for effective water splitting

J. Catal.

(2019)

P.Y. Zhang et al.

Design of plasmonic CuCo bimetal as a nonsemiconductor photocatalyst for synchronized hydrogen evolution and storage

Appl. Catal. B-Environ.

(2019)

H.Y. Wang et al.

Boosting photocatalytic hydrogen evolution achieved by rationally designed/constructed carbon nitride with ternary cobalt phosphosulphide

J. Colloid Interf. Sci.

(2019)

C.Y. Wang et al.

Enhanced hydrogen production from ammonia borane over CuNi alloy nanoparticles supported on TiO₂ (B)/anatase mixed-phase nanofibers with high specific surface area

J. Alloy Compd.

(2020)

M. Hojamberdiev et al.

Synergistic effect of g-C₃N₄, Ni(OH)₂ and halloysite in nanocomposite photocatalyst on efficient photocatalytic hydrogen generation

Renew. Energ.

(2019)

X.Z. Yue et al.

Synergistic effect based Ni_xCo_1-x architected Zn_0.75Cd_0.25S nanocrystals: An ultrahigh and stable photocatalysts for hydrogen evolution from water splitting

Appl. Catal. B-Environ

(2018)

T. Simon et al.

Redox shuttle mechanism enhances photocatalytic _H2 generation on Ni-decorated CdS nanorods

Nat. Mater.

(2014)

T. Wang et al.

Ni-Mo Nanocatalysts on N-Doped Graphite Nanotubes for Highly Efficient Electrochemical Hydrogen Evolution in Acid

ACS Nano

(2016)

Cited by (17)

Fabrication of CuMnO<inf>2</inf>/XMoO<inf>4</inf> (X=Ni, Co, Fe) heterostructure for hydrogen evolution under visible light irradaiation
2024, International Journal of Hydrogen Energy
CuMnO₂/XMoO₄ (X=Ni, Co, Fe) is a novel high-efficiency photocatalyst, which was synthesized by electrostatic self-assembly method. Under visible light irradiation, by comparing with other eighth main group metals (Fe, Co), it was found by experimental study that adding 30 mg of CuMnO₂ to 100 mg of NiMoO₄ (CuMnO₂/NiMoO₄-30%), it has the best hydrogen evolution effect up to 300 μ mol, which is 1.49 and 2.88 times more effective than CuMnO₂/CoMoO₄ and CuMnO₂/FeMoO₄ respectively. Meanwhile, the hydrogen evolution yield of CuMnO₂/NiMoO₄ was about 4 times that of CuMnO₂ and NiMoO₄. The photoelectrochemical and time-resolved fluorescence experiments confirmed the excellent charge separation efficiency of the composite catalyst, and the linear voltammetry curve showed that the composite catalyst had the characteristics of high current response. When CuMnO₂ is loaded on NiMoO₄, CuMnO₂/NiMoO₄ exhibits excellent photocatalytic activity due to the formation of Type I heterojunction, which promote charge transfer and effectively improve the separation of electrons and holes. This experiment provides a simple and feasible idea for the study of composite catalysts with high catalytic activity.
Coupling of Sm<inf>2</inf>WO<inf>6</inf> and ZIF-67 to form S–scheme heterojunction to improve the performance of photocatalytic hydrogen production
2024, International Journal of Hydrogen Energy
Photocatalytic hydrogen production was a potential strategy to solve energy shortage and environmental pollution. One of the valuable research directions for improving photocatalytic efficiency was to prepare catalysts in an efficient and low-cost way. Lamellar Sm₂WO₆ and dodecahedron Zeolitic Imidazolate Framework-67 (ZIF-67) have been prepared successfully based on morphology control. Sm₂WO₆/ZIF-67 was prepared by a novel in situ growth scheme, which was confirmed by crystal structure, morphology and elemental composition analysis. The close interaction between Sm₂WO₆ and ZIF-67 was confirmed by photoelectrochemical measurements. Based on the design of band structure, the S-type heterojunction was constructed. The research results of this paper provided a reference for exploring non-noble metal composite materials and demonstrated great potential in photocatalytic.
Efficient photothermal catalytic CO<inf>2</inf> reduction over in situ construction ZnIn<inf>2</inf>S<inf>4</inf>@Ni(OH)<inf>2</inf>/NiO Z-scheme heterojunction
2024, Chemical Engineering Journal
Photocatalytic reduction of CO₂ into valuable chemicals has been considered as a sustainable and environmentally friendly technology, which can simultaneously alleviate the energy crisis and environmental problems that have puzzled people for a long time. Herein, we successfully synthesize defective ZnIn₂S₄@Ni(OH)₂/NiO (ZIS@NOH/NiO) Z-scheme heterojunction photocatalysts through solvothermal and low-temperature calcination strategies. The loading of Ni(OH)₂ nanosheets can increase the specific surface area of photocatalyst, and form Z-scheme heterojunction with ZIS to improve the utilization of photogenerated electrons. It is worth noting that during the low-temperature calcination process, Ni(OH)₂ is partially converted into NiO, and a large number of metal defects are formed, which reduces the bandgap of Ni(OH)₂ and shows visible light response. In addition, the generated black defective NiO with full spectrum response and good photothermal effects can accelerate the migration of photogenerated carriers and reduce the catalytic reaction barrier of CO₂. Consequently, the prepared ZIS@NOH/NiO exhibits a high yield (133.74 μmol g⁻¹) and selectivity (86.2 %) for CO₂ to CH₄, which almost is 3.2 and 11.1 times than those of ZnIn₂S₄@Ni(OH)₂ and ZnIn₂S₄, respectively. Furthermore, in-situ Fourier transform infrared spectroscopy (FTIR) analysis reveal the effective adsorption of CO₂ on the ZnIn₂S₄@Ni(OH)₂/NiO surface and the high selectivity of CH₄. This work will provide meaningful prospects for designing a carbon dioxide reduction photocatalyst with high conversion and selective.
Multifunctional Ni(OH)<inf>2</inf>/Ag composites for ultrasensitive SERS detection and efficient photocatalytic degradation of ciprofloxacin and methylene blue
2024, Talanta
To enable the widespread application of surface-enhanced Raman scattering (SERS) technique in practical sensing of organic pollutants, it is essential to develop a reliable SERS substrate that offers both high sensitivity and reusability. In this study, we employed a simple and rapid in-situ deposition method to coat Ag nanoparticles onto flower-like Ni(OH)₂ spheres, resulting in the formation of Ni(OH)₂/Ag composites with excellent photocatalytic performance and SERS activity. These composites were used as a promising SERS analysis tool for effective detection of organic pollutants, including ciprofloxacin hydrochloride (CIP) and methylene blue (MB). Notably, the composites exhibited outstanding detection limits of 10⁻⁸ M for MB and 10⁻⁷ M for CIP, respectively, and showed a strong linear relationship between SERS intensities and the logarithmic concentration (R² ≥ 0.97). Moreover, under simulated sunlight irradiation, the Ni(OH)₂/Ag composites efficiently degraded MB and CIP molecules within a short period of 120 min for MB and 130 min for CIP. This demonstrated their practical reusability, as evidenced by their consistent performance over five cycles of SERS sensing. These findings underscore the significant potential of these composites for SERS-based detection of trace pollutants and ecological restoration through photocatalytic reactions in the future.
Up–conversion and Landau damping effect of Ni<inf>1–x</inf>Nd<inf>x</inf>(OH)<inf>2</inf>/Ti<inf>3</inf>C<inf>2</inf> to improve the selectivity of thermal coupled photocatalytic reduction of CO<inf>2</inf>
2023, Ceramics International
Photocatalysis is currently used to enhance CO₂ conversion, while improving selectivity is challenging. Herein, Ni_1–xNd_x(OH)₂/Ti₃C₂ consisting of Nd³⁺–doped in β–Ni(OH)₂ and Ti₃C₂-MXene was prepared for the selective reduction of CO₂ to CO by thermal coupled photocatalytic. The effect of the introduction of the up–conversion effect is (1) to increase the concentration of photogenerated electrons and (2) to increase the catalyst surface temperature. The increased concentration of photogenerated electrons leads to an enhanced Landau damping effect, thus the number of high-energy hot electrons supplementing the Ti₃C₂ increases. The valence band upward shift reduces the ability of Ni_1–xNd_x(OH)₂/Ti₃C₂ to dissociate H₂. The increased surface temperature of the catalyst and the reduced dissociation of H₂ facilitate the thermal coupled photocatalytic reduction of CO₂ to CO. A maximum CO yield of 532.9 μmol·g_cat.⁻¹·h⁻¹ and CO selectivity of 82.5% was realized on the Ni_0.56Nd_0.01(OH)₂/Ti₃C₂.
Nickel-based tungstate supported with different forms of SnS<inf>2</inf> to achieve improved photocatalytic performance
2023, Journal of Alloys and Compounds
Semiconductor materials have been applied in many research directions such as photoelectrocatalysis, and shortening the electron transport pathway by coupling semiconductors is an effective path to promote the capability of photocatalytic hydrogen-producing. The crystalline SnS₂ and amorphous SnS₂ were combined with NiWO₄ respectively, in the respective optimal hydrogen-producing conditions, it was 298.6 μmol for SnS₂/NiWO₄ (amorphous J-SnS₂ and NiWO₄) and 228.5 μmol for J-SnS₂ NiWO₄ (crystalline SnS₂ and NiWO₄). A series of characterization results showed that SnS₂/NiWO₄ showed better photocatalytic hydrogen-producing performance than J-SnS₂/NiWO₄ under the same test conditions. The catalysts SnS₂ and NiWO₄ were constructed into p-n type heterojunction SnS₂/NiWO₄ by electrostatic self-recombination. SEM, XRD and electrochemical tests demonstrate that the high hydrogen-producing performance of SnS₂/NiWO₄ is due to the establishment of p-n heterojunction, which enhances the electron transport efficiency. The experimental data were used to test the photocatalytic hydrogen-producing activity of SnS₂/NiWO₄ with the control variable method, then it was proved that the photocatalytic hydrogen-producing volume of SnS₂/NiWO₄ reached 298.6 μmol in 5 h, which was 3.51 times that of NiWO₄ at 5 h hydrogen-producing of 85 μmol. The morphology of nanoparticles NiWO₄ attached to a smooth surface sphere SnS₂ provides a larger specific surface area and more reactive sites for the photocatalytic eosin hydrogen-producing system, in addition the establishment of p-n type heterojunction structure effectively improves the utilization rate of the sacrificial TEOA and photosensitizer EY, thereby improving the hydrogen-producing performance of SnS₂/NiWO₄, which offers a feasible policy for photocatalytic efficient hydrogen-producing technology.

View all citing articles on Scopus

View full text

Full Length ArticleHighly efficient photocatalytic hydrogen evolution driven by adjustable bimetal CuNi derived hexagonal Ni(OH)2

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Catalyst synthesis

Structures and characterizations

Conclusion

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgements

NANO Energy

Int. J. Hydrogen Energy

Appl. Catal. B

Renewable Energy

Appl. Catal. B

NANO Energy

Carbon

NANO Energy

Appl. Catal. B – Environ.

Appl. Catal. B-Environ.

J. Catal.

Appl. Catal. B-Environ.

J. Colloid Interf. Sci.

J. Alloy Compd.

Renew. Energ.

Appl. Catal. B-Environ

Redox shuttle mechanism enhances photocatalytic H2 generation on Ni-decorated CdS nanorods

Nat. Mater.

Ni-Mo Nanocatalysts on N-Doped Graphite Nanotubes for Highly Efficient Electrochemical Hydrogen Evolution in Acid

ACS Nano

Full Length Article
Highly efficient photocatalytic hydrogen evolution driven by adjustable bimetal CuNi derived hexagonal Ni(OH)₂

Redox shuttle mechanism enhances photocatalytic _H2 generation on Ni-decorated CdS nanorods