Cu-clusters nodes of 2D metal-organic frameworks as a cost-effective noble-metal-free cocatalyst with high atom-utilization efficiency for efficient photocatalytic hydrogen evolution

Jiang, Guangmei; Liu, Xingyan; Jian, Huilong; Lu, Pei; Bai, Jinwu; Zhang, Guizhi; Wen, Yun; Li, Siqi; He, Youzhou

doi:10.1016/j.cclet.2021.09.047

Cited by 22 publications

(10 citation statements)

References 45 publications

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“…Micro- and nanosized porphyrin-based MOFs, ,,− ,,,− MOF/COF composites, and COFs − have been thoroughly investigated and are found to be efficient photocatalysts for H 2 evolution, where the porphyrin or metalloporphyrin chromophore acts as a photosensitizer through either energy or electron transfer. This process triggers the donation of e – from the charge-separated state to the proton, followed by filling of the hole using a sacrificial electron donor.…”

Section: Photocatalytic H2 Evolutionmentioning

confidence: 99%

“…A noble-metal-free, cost-effective, and high-performing nanophotocatalyst for H 2 evolution was recently reported . The 2D-MOF (NS-Cu) was prepared solvothermally, and its structure (Figure a) was identified by powder X-ray diffraction (PXRD).…”

Section: Photocatalytic H2 Evolutionmentioning

confidence: 99%

“…A noble-metal-free, cost-effective, and high-performing nanophotocatalyst for H 2 evolution was recently reported. 148 The 2D-MOF (NS-Cu) was prepared solvothermally, and its structure (Figure 15 a) was identified by powder X-ray diffraction (PXRD). TEM (Figure 15 b) was used along with scanning electron microscopy (SEM) to characterize the flowershaped particles, and the thickness (15 nm) of the nanosheets was measured by atomic force microscopy (AFM).…”

Section: Semiconducting Materialsmentioning

confidence: 99%

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Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Asselin

Harvey

2022

ACS Appl. Nano Mater.

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Porphyrin-based materials are excellent chromophores because they strongly absorb visible light and their relatively low-energy lowest unoccupied molecular orbitals thermodynamically favor photoinduced electron transfer. They can generate charge-transfer excited states with and without cocatalyst(s) and ease energy transfer and ultrafast excitation energy migration. Combined with synthetic accessibility, these qualities make them ideal building blocks for porous metal− organic framework (MOF)-and covalent−organic framework (COF)-based photocatalysts to produce solar fuels. This review first describes the structures of the most common porphyrinic MOFs and COFs and their excited-state properties and semiconducting behavior as well as that of derived composites. The generally accepted mechanisms of formation of H 2 , CH 4 and derivatives, and N 2 are then reviewed, followed by the detailed examples of nano-MOFs and nano-COFs used for the said purpose: characteristic parameters such as rates of production, turnover numbers (TONs), turnover frequencies (TOFs), and apparent quantum efficiencies are described and compared. This shows that porphyrin-based MOFs and COFs are efficient solar-fuelproducing photocatalysts, with characteristics comparable to those of nonporphyrinic MOF and COF photocatalysts, although, on some occasions, the rates of production fall short of record values. Conversely, porphyrinic MOFs and COFs exhibit the greatest TONs and TOFs of any solar-fuel-producing MOFs or COFs but still face shortcomings concerning selectivity in CH 4 production because of the many possible side products. Importantly, while the best rate of photoproduction of solar fuels has been observed from nanoscale photocatalysts, there seem to be no drastic differences in the rate (within μmol −1 h −1 and mmol g −1 h −1 ) between nanoscale and microscale heterogeneous photocatalysts. This observation suggests that the more active sites are mostly located at or near the surface of the particles. Overall, nanosized porphyrin-based MOFs and COFs show rich and promising photocatalytic properties for generating solar fuels but still have room for improvement.

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Section: Photocatalytic H2 Evolutionmentioning

confidence: 99%

Section: Photocatalytic H2 Evolutionmentioning

confidence: 99%

Section: Semiconducting Materialsmentioning

confidence: 99%

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Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Asselin

Harvey

2022

ACS Appl. Nano Mater.

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“…As an ecology-reliable approach to meet the need of human society development, photocatalytic hydrogen evolution (PHE) currently is endowed huge expectations in addressing the problems of solar energy capture and storage. − However, prominent PHE is still restricted by the insightful apprehension of photocatalytic thermodynamics and kinetics, in other words, the necessary modulation of photogenerated electrons and holes. − Electrons participate in hydrogen production directly; therefore, the behavior of electrons is widely investigated and numerous studies were attributed to successful modulation of electrons. Nevertheless, the slow transfer rate of holes (which is approximately two to three orders of magnitude slower than that of electrons , ) and the sluggish kinetics of the oxidative reaction (typically oxidation of water) easily make holes accumulate and recombine with electrons, which lead to the amount of electrons involved in proton reduction decreasing remarkably.…”

Section: Introductionmentioning

confidence: 99%

Revealing the Importance of Hole Transfer: Boosting Photocatalytic Hydrogen Evolution by Delicate Modulation of Photogenerated Holes

Xiang

et al. 2023

ACS Catal.

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Photocatalytic hydrogen evolution (PHE) has gained massive attention for the development of renewable resources. Currently, prominent and stable PHE is still restricted by the limited utilization of photocatalytic charge carriers, especially holes, of which the transfer rate is approximately two to three orders of magnitude slower than that of electrons. Although it is widely accepted that surface holes can be consumed by electron donors, the rational design of photocatalysts to speed up hole transfer and understand the ultrafast photodynamics as well as the exploration of the effect of oxidation products is still highly urgent. Herein, cadmium sulfide (CdS), as the model photocatalyst, is investigated for prominent PHE based on hole modulation strategies. To accelerate the surface reaction, H2S-saturated Na2S&Na2SO3 solution, which outperforms traditional hole scavengers, is selected to remove the holes accumulating on the photocatalyst surface, while the oxidative cocatalyst palladium sulfide (PdS) is simultaneously impregnated on CdS to optimize the hole transfer process. Evidenced by femtosecond transient absorption spectroscopy (TAS) and band structure analysis, the ultrafast process (1–5 ps) highly related with hole transfer from CdS to PdS is proved in the CdS/PdS composite. More importantly, density functional theory (DFT) calculation suggests that the hole accumulation site (PdS) is also the oxidation active site where the active species (HS*) adsorbs on. Finally, the oxidation product composition is analyzed through Fourier transform infrared (FTIR) spectroscopy, which indicates that the colorless and value-added product S2O3 2– protects the photocatalyst from the light shielding effect. Contributed by factors mentioned above, improved PHE efficiency (∼145.9 mmol·g–1·h–1) is achieved on the CdS/PdS composite.

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“…On the other hand, the derivatized porphyrins can be used as building blocks to construct porous polymers, such as coordination polymers and porous organic polymers (POPs) [ 16 , 17 , 18 , 19 ]. The above-mentioned factors are meaningful to effectively modulate the catalytic features of porphyrins, making them excellent candidate catalysts for many processes, such as organic chemical reactions, ORR, HER, CO 2 reduction reaction (CO 2 RR), and of course, OER [ 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ].…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Porphyrin-Based Systems for Electrochemical Oxygen Evolution Reaction

Yao

Wang

et al. 2022

IJMS

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Oxygen evolution reaction (OER) plays a pivotal role in the development of renewable energy methods, such as water-splitting devices and the use of Zn–air batteries. First-row transition metal complexes are promising catalyst candidates due to their excellent electrocatalytic performance, rich abundance, and cheap price. Metalloporphyrins are a class of representative high-efficiency complex catalysts owing to their structural and functional characteristics. However, OER based on porphyrin systems previously have been paid little attention in comparison to the well-described oxygen reduction reaction (ORR), hydrogen evolution reaction, and CO2 reduction reaction. Recently, porphyrin-based systems, including both small molecules and porous polymers for electrochemical OER, are emerging. Accordingly, this review summarizes the recent advances of porphyrin-based systems for electrochemical OER. Firstly, the electrochemical OER for water oxidation is discussed, which shows various methodologies to achieve catalysis from homogeneous to heterogeneous processes. Subsequently, the porphyrin-based catalytic systems for bifunctional oxygen electrocatalysis including both OER and ORR are demonstrated. Finally, the future development of porphyrin-based catalytic systems for electrochemical OER is briefly prospected.

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Cu-clusters nodes of 2D metal-organic frameworks as a cost-effective noble-metal-free cocatalyst with high atom-utilization efficiency for efficient photocatalytic hydrogen evolution

Cited by 22 publications

References 45 publications

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Revealing the Importance of Hole Transfer: Boosting Photocatalytic Hydrogen Evolution by Delicate Modulation of Photogenerated Holes

Recent Advances in Porphyrin-Based Systems for Electrochemical Oxygen Evolution Reaction

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