Porphyrin-based Ti-MOFs conferred with single-atom Pt for enhanced photocatalytic hydrogen evolution and NO removal

Feng, Hongqing; Li, Houfan; Liu, Xingyan; Huang, Yumin; Qian, Ping; Peng, Rong; Du, Ruoyu; Zheng, Xiaohui; Zhang, Yin; Li, Siqi; He, Youzhou

doi:10.1016/j.cej.2021.132045

Cited by 45 publications

(28 citation statements)

References 45 publications

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“…It is noteworthy that N 1s spectra shift to higher binding energy, attributing to the formation of possible Pt-N coordination after Pt metal loading. [16] Interestingly, we note that after depositing Pt single atom, the contents of the latter two are significantly lowered down to 6.90 and 4.70 at% compared with pristine VN support (10.90 and 9.99 at%), as shown in the inset of Figure 3e. These consumed N species are possibly the result of the coordination with Pt atoms.…”

Section: Fabrication Of Single-atom Pt 1 -Vn Catalystmentioning

confidence: 76%

Role of N in Transition‐Metal‐Nitrides for Anchoring Platinum‐Group Metal Atoms toward Single‐Atom Catalysis

Cheng

Shi

et al. 2022

Small Methods

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Single‐atom catalysts (SACs) with a maximum atom utilization efficiency have received growing attention in heterogeneous catalysis. The supporting substrate that provides atomic‐dispersed anchoring sites and the local electronic environment in these catalysts is crucial to their activity and stability. Here, inspired by N‐doped graphene substrate, the role of N is explored in transition metal nitrides for anchoring single metal atoms toward single‐atom catalysis. A pore‐rich metallic vanadium nitride (VN) nanosheet is fabricated as one supporting‐substrate example, whose surface features abundant unsaturated N sites with lower binding energy than that of widely used N‐doped graphene. Impressively, it is found that this support can anchor nearly all platinum‐group single atoms (e.g., platinum, palladium, iridium, and ruthenium), and even be extendable to multiple SACs, i.e., binary (Pt/Pd) and ternary (Pt/Pd/Ir). As a proof‐of‐concept application for hydrogen production, Pt‐based SAC (Pt1‐VN) performs excellently, exhibiting a mass activity up to 22.55 A mg−1Pt at 0.05 V and a high turnover frequency value close to 0.350 H2 s−1, superior to commercial platinum/carbon catalyst. The catalyst's durability can be further improved by using binary (Pt1Pd1‐VN) SAC. This work provides inexpensive and durable nitride‐based support, giving a possible pathway for universally constructing platinum‐group SACs.

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Section: Fabrication Of Single-atom Pt 1 -Vn Catalystmentioning

confidence: 76%

Role of N in Transition‐Metal‐Nitrides for Anchoring Platinum‐Group Metal Atoms toward Single‐Atom Catalysis

Cheng

Shi

et al. 2022

Small Methods

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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%

“…He and collaborators have reported a robust and efficient titanium/Pt(TCPP)-based nano-MOF denoted as TMF-Pt (Figure ). This MOF was obtained by combining Ti(OBu) 4 , Pt(TCPP), and benzoic acid in DMF at 150 °C (423 K) for 5 days and then recovered by centrifugation. The PXRD pattern was consistent with that of the structure depicted in Figure a.…”

Section: Photocatalytic H2 Evolutionmentioning

confidence: 99%

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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“…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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Porphyrin-based Ti-MOFs conferred with single-atom Pt for enhanced photocatalytic hydrogen evolution and NO removal

Cited by 45 publications

References 45 publications

Role of N in Transition‐Metal‐Nitrides for Anchoring Platinum‐Group Metal Atoms toward Single‐Atom Catalysis

Role of N in Transition‐Metal‐Nitrides for Anchoring Platinum‐Group Metal Atoms toward Single‐Atom Catalysis

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

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

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