Oriented assembly of metal-organic frameworks and deficient TiO2 nanowires directed by lattice matching for efficient photoreversible color switching

ACS Appl. Energy Mater.

Cao

Luo

et al. 2022

Self Cite

Rational design of heterojunctions as photocatalysts that can help alleviate the energy and environmental crisis relies on the efficient electron transfer to the catalytically active sites. In this work, a robust metal–organic framework (MOF)-based heterostructured catalyst for the CO2 reduction reaction (CRR) was reported, taking advantage of a synergy effect between ultrathin (1.5 nm thickness) Ni-rich Ni(OH)2 nanosheets (NSs) and the highly stable and conductive Fe-rich Prussian blue (PB). This Ni(OH)2/PB photocatalyst can attain an optimal CO evolution rate of 108.8 mmol h–1 g–1 and a high CO selectivity (88.2–95.0%) in the CRR. The stable PB helps atomically thin Ni(OH)2 NSs to be well-dispersed and exposed in the heterojunction. A built-in electric field found at the interface of the bulk-sized PB and the ultrathin Ni(OH)2 further directs the electron transfer. Intriguingly, the conductive PB can quickly capture the electrons from the Ru-based photosensitizer and then rapidly sends them to the CRR-active Ni(OH)2 in the Z-scheme Ni(OH)2/PB system, accounting for its high efficiency and high selectivity over CO2 reduction into CO. The findings underline the versatility and the mechanistic response of MOFs in constructing advanced catalysts.

Section: Resultsmentioning

confidence: 99%

Built-In Electric Field Directs Electron Transport at Ultrathin Ni(OH)₂/Metal–Organic Framework Interface for Efficient Photocatalytic CO₂ Reduction

ACS Appl. Energy Mater.

Cao

Luo

et al. 2022

Self Cite

“…[217] In this aspect, lattice-match effect could drive the oriented assembly of nanounits, offering a facile and powerful tool to the creation of well-defined heterointerface with defined atomic configuration and regulated defect structure. [169,185] As emerging heterogeneous materials, the single-atom catalysts (SACs) have witnessed their great superiority for field applications, [165,166,218,219] which heavily relies on a controllable regulation of the metal active sites and surrounding microenvironment of single atoms in SACs heterostructures. As such, Zhou et al [220] prepared a heterostructure comprising NiO/Ni deposited on Ag NWs via electrodeposition strategy, and thereafter the single-atom Pt can be anchored selectively on interface of NiO/Ni.…”

Section: Perspective and Challengementioning

confidence: 99%

mentioning

confidence: 99%

Toward Rational Design of Ordered Heterostructures for Energy and Environmental Sustainability: A Review

Zhang

Yang

Adv Energy and Sustain Res

et al. 2023

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Precise synthesis of high‐quality, sophisticated heterostructures by ordered assembly of small nanomaterials is a key step to gain advanced materials that have elaborate functionalities, collective properties, and enhanced stabilities for mitigating the energy and environment crisis. Intricating in the structure, size, and shape of nanomaterials, ordered assembly of isotropic or anisotropic nanoscale building blocks to create specified heterostructures remains challenging, owing to the extraordinary challenges in design of lattice topology of distinct nanounits and in control of their crystallization, growth, and assembly mechanism/kinetics. Herein, the emerging methodologies to prepare a diversity of ordered heterostructures with strengthened particle–particle interaction are examined and synergistic properties are enhanced. It is aimed to unlock the principles to regulate the geometrical and electronic properties of these intriguing kinds of heterostructures for respective sustainable energy and environmental applications. Current challenges and opportunities in customization of ordered heterostructure at the nanoscale and atomic level are also discussed.

“…The FeNi x PBA catalysts, where x denotes the molar ratio of Ni to Fe in the PBA framework, were prepared using NiC 4 H 6 O 4 •4H 2 O and K 4 Fe(CN) 6 •3H 2 O by co-precipitation at 80 °C from distilled water with the assistance of PVP. 34 All FeNi x PBAs have identical X-ray diffraction (XRD) patterns (Figure 1b) that can be identified as the cubic phase PBA (JCPDS no. 86-0501), 35 and no additional Fe-based or Nibased impurity phase can be found.…”

Section: Tailoring the Ni/fe Ratio Of Bimetallic Feni X Pbamentioning

confidence: 99%

Trade-Off of Metal Sites in Fe–Ni Bimetal Metal–Organic Frameworks for Efficient CO₂ Photoreduction with Nearly 100% CO Selectivity

ACS Appl. Mater. Interfaces

Luo

Zhang

et al. 2022

Self Cite

This work disclosed the trade-off effect of two metal sites, which display distinct, key functionalities in naturally occurring and artificial catalysts for developing an advanced CO 2 reduction system. To exploit the metal−organic frameworks (MOFs) as advanced catalysts, we prepared a series of Prussian blue analogues (FeNi x PBAs) of tunable Ni/Fe molar ratio without changing the oxidation state of Fe and Ni for use as a photocatalyst in the CO 2 reduction reaction (CRR). The FeNi 0.66 PBA gives a superior CO yield rate (14.28 mmol•g −1 • h −1 ) with nearly 100% CO selectivity, but the PBA would be basically CRR-inactive without either Ni or Fe. Experimental and calculation studies demonstrate that Fe and Ni display distinct functionalities. Specifically, Fe is an efficient mediator that boosts the electron transfer both from the photosensitizer to FeNi x PBA and from FeNi x PBA to CO 2 , and Ni serves as the active site for CO 2 adsorption and reduction. Intriguingly, when there is already sufficient Ni in the catalyst, further increase of the Ni content gives marginal gains in the CO 2 adsorption affinity that cannot offset the weakened electron transfer due to the Ni excess. The findings can help advance the design of bimetallic MOF catalysts that mimic naturally occurring bimetallic catalysts.