Ultrathin Metal-organic Framework Research Articles

Ultrathin metal–organic framework synergizes with carbon quantum dots improving photoelectrochemical water oxidation and tetracycline hydrochloride degradation performance

Ultrathin metal–organic framework synergizes with carbon quantum dots improving photoelectrochemical water oxidation and tetracycline hydrochloride degradation performance

Designing 1-nm-Thick MOF Nanosheets with Donor-Acceptor Complexes for Photosynthesis of H2O2 Using Water and Dioxygen Only.

Artificial photosynthesis of hydrogen peroxide (H2O2) presents a promising environmentally friendly alternative to the industrial anthraquinone process. This work designed ultrathin metal-organic framework (MOF) nanosheets on which porphyrin ligand as an electron donor (D) and anthraquinone (AQ) as an electron acceptor (A) are integrated as the D-A complexes. The porphyrin component allows the MOF nanosheets to absorb full-spectrum solar light while the acceptor AQ motif promotes central aluminum ion coordination, hindering layer stacking to achieve a thickness of 1.0 nm. The ultrathin D-A design facilitates the separation of electrons from the MOF skeleton to the AQ motif, which induces the direct two-electron oxygen reduction reaction (ORR) mediated by the reversible redox couple of AQ-AQH2 and multielectron water oxidation reaction (WOR) driven by holes remaining on the porphyrin part. In O2-saturated water, the ultrathin MOF nanosheets outperformed the AQ-free bulk and multilayered counterparts by 2.9 and 2.6 times in H2O2 production, respectively, achieving the apparent quantum yield of 4.8% at 420 nm. It also surpasses other benchmark photocatalysts, including the typical MOF photocatalyst, MIL-125-NH2, and organic polymeric photocatalysts. The ultrathin D-A MOF photocatalyst generated H2O2 via both two-electron ORR as a major path and two-electron WOR as a minor path. This approach presents a promising strategy for the rational design of efficient nanostructured photocatalysts for solar fuels and chemicals.

Enhancing the charge storage capacity of ultrathin metal–organic framework nanosheets with CO2-derived carbon nanotubes

Metal-organic frameworks (MOFs) hold promise as efficient electrode materials for supercapacitors, but their practical application is hindered by the intrinsic low electrical conductivity. Here, we employ CO2-derived carbon nanotubes based on molten salt electrolysis (MSE-CNTs) as the framework to guide the growth of nickel-based MOF (Ni-MOF). The resulting MSE-CNTs/Ni-MOF composite exhibits an impressive specific capacitance of 1714.2 F g−1 at 1 A g−1, 1.45 and 1.26 times greater than bare Ni-MOF (1185.7 F g−1) and CVD-CNTs/Ni-MOF (1364.3 F g−1, the composite of Ni-MOF and commercial CNTs produced by chemical-vapor-deposition), respectively. Moreover, the assembled hybrid supercapacitor (MSE-CNTs/Ni-MOF//active carbon) achieves a remarkable specific capacitance of 136.5 F g−1 at 1 A g−1 and an energy density of 54.8 Wh kg−1 at 850 W kg−1, standing among the best of the state-of-the-art. The superior capacitive performance of MSE-CNTs/Ni-MOF than CVD-CNTs/Ni-MOF can be attributed to the better electrical conductivity of MSE-CNTs, the thinner nanosheet architecture of MSE-CNTs/Ni-MOF, and the effective electrically conductive network within the composite. This work marks a paradigm shift from greenhouse gas CO2 to excellent energy storage materials, paving the way for addressing both the energy and climate issues simultaneously.

Enhanced overall water splitting by morphology and electronic structure engineering on pristine ultrathin metal-organic frameworks

Metal-organic frameworks (MOFs) have caused extensive attention attributed to their widespread applications including electrocatalysis by virtue of their distinctive structural characteristics. However, the direct application of pristine MOFs as bifunctional electrocatalysts is quite challenging due to their insufficient active sites and poor electrical conductivity. In this research, the ultrathin tri-metal (Fe, Co, and V) doped FeCoV-NiMOF nanosheet arrays were prepared through a facile hydrothermal method. Benefiting from the distinctive ultrathin (1.5 nm) nanosheet arrays and electronic structure reconfiguration induced by heteroatom doping, the prepared FeCoV-NiMOF displays the low overpotentials of 238, 309, and 408 mV for oxygen evolution reaction (OER) and 144, 255, and 349 mV for hydrogen evolution reaction (HER) at the current densities of 10, 100, and 1000 mA cm−2, respectively, outperforming the vast majority of previously reported bifunctional pristine MOFs. The electrolytic cell utilizing FeCoV-NiMOF as both cathode and anode requires just 1.61 V to attain 10 mA cm−2 and displays superior stability of 100 h at 100 mA cm−2. In the anion exchange membrane electrolyzer, as-prepared FeCoV-NiMOF needs a low cell voltage of 2.16 V at 500 mA cm−2 for effective overall water splitting, demonstrating its substantial potential as bifunctional electrodes for H2 production. The viable and efficient strategy in this study exhibits great prospects to enrich the exploration of bifunctional MOF-based electrocatalysts with superior performance for renewable energy conversion.

In situ coordinated ultrathin MOF-polymer electrolyte membrane with vertically aligned transfer channels for solid lithium metal batteries

Metal organic framework (MOF)-polymer composite solid electrolyte membrane with novel microstructure is expected to show attractive prospect for solid state lithium metal batteries. But the reported MOF were usually regarded as an entirety in composite solid electrolyte resulting in tradeoff between ionic conductivity and lithium dendrite inhibition ability. Herein, MOF-polymer composite membrane with vertically aligned channels and ultrathin MOF layer is proposed to decrease lithium ion transportation resistance obtained by simple phase inversion and in situ coordinated growth methods. The vertically aligned highways can decrease tortuous pathways and intensify ion conduction. The embedded ultrathin MOF layer on membrane surface leads to homogeneous plating/stripping of lithium. This novel structured MOF-polymer composite solid electrolyte exhibits improved ionic conductivity of 0.55 mS cm−1 at 22 ° C and lithium ion transference number of 0.87. Furthermore, the Li/Li symmetrical cell shows stable lithium plating/stripping performance for 1100 h at 0.1 mA cm−2 and 0.1 mA h cm−2. LiFePO4/MOF-polymer/Li coin battery demonstrates good rate capability and cycling performance with capacity retention of 82 % after 100 cycles at 0.2C and the pouch cell can light up the “DLUT” blue light lamp under folding and cutting states. This work encourages a new avenue to develop composite solid electrolytes with ion transportation highways and uniform distribution plane for solid lithium metal batteries.

Ultrathin metal-organic framework nanosheets (Cu-TCPP) assembled micro flower combined with endonuclease signal amplification for ultrasensitive detection

Metal-organic framework play an important role in developing novel detection techniques. Herein, an ultrathin two-dimensional (2D) metal-organic framework nanosheet (Cu-TCPP) assembled microflower was successfully synthesized and applied for ultrasensitive detection. The high detection performance of Cu-TCPP microflower was attributed to high-capacity aptamer adsorption and specific desorption resulting from numerous approachable active sites, and its ultrathin nanosheets microflower-like structure. Moreover, the Cu-TCPP microflower had overcame the disadvantages of 2D MOF nanosheets which tended to agglomerate. Moreover, it exhibited excellent fluorescence quenching performance as a donor for fluorescence resonance energy transfer. Acetamiprid, a new chloronicotinic neurotoxic insecticide was used as the model analyte. The ultrasensitive sensor was developed by combining the Cu-TCPP microflower with deoxyribonuclease Ⅰ signal enhanced fluorescence. When acetamiprid was present, the fluorescent labeled aptamer probe was selectively bound to acetamiprid and desorbed from the Cu-TCPP microflower, resulting in fluorescence recovery. Subsequently, DNase Ⅰ was used to cleave the DNA strands of the aptamer probe, and acetamiprid was released to participate in a new cycle. The detection limit of the assay was as low as 5.56 pg/mL with a linear range 50.00 pg/mL∼5.00 μg/mL, and it was a universal platform to detect other analytes.

Preparation of a Nanosheeted Uranyl-Organic Framework for Enhanced Photocatalytic Oxidation of Toluene.

Preparation of ultrathin metal-organic framework (MOF) nanosheets is an effective way to improve the catalytic efficiency of MOF photocatalysts owing to their superiority in reducing the recombination rate of photogenerated electrons and holes and enhancing charge transfer. Herein, a light-sensitive two-dimensional uranyl-organic framework named HNU-68 was synthesized. Due to its interlayer stacking structure, the corresponding ultrathin nanosheets with a thickness of 4.4 nm (HNU-68-N) can be obtained through ultrasonic exfoliation. HNU-68-N exhibited an enhanced ability to selectively oxidize toluene to benzaldehyde, with the value of turnover frequency being approximately three times higher than that of the bulk HNU-68. This enhancement is attributed to the smaller size and interface resistance of the layered HNU-68-N nanosheets, which facilitate more thorough substrate contact and faster charge transfer, leading to an improvement in the photocatalytic efficiency. This work provides a potential candidate for the application of ultrathin uranyl-based nanosheets.

Asymmetric ionogel electrolyte with an ultrathin metal–organic framework layer for lithium dendrite inhibition in solid-state lithium-metal batteries

Solid-state electrolytes (SSEs) are used to prevent internal short circuits caused by the growth of lithium dendrites in solid-state lithium-metal batteries (SSLMBs). Ionogel electrolytes are new polymeric SSEs with outstanding processability, excellent flexibility, and superior ionic conductivity. Lithium-ion transport in ionogel electrolytes depends on ionic liquid (IL) content; however, increasing the IL content improves ionic conductivity but sharply decreases mechanical properties, thus limiting the ability to resist lithium dendrites. Thus, ionogel electrolytes must strike a balance between ionic conductivity and mechanical properties. Herein, we adopt a new strategy to suppress the growth of lithium dendrites by in situ polymerizing an ultrathin metal–organic framework (MOF) layer (9.8 μm) onto a highly ionic conductive ionogel electrolyte. The ionogel electrolyte provides an asymmetric SSE (ASSE) with a remarkable ionic conductivity of 4.8 × 10−4 S cm−1 (30 °C), whereas the ultrathin MOF layer regulates uniform dissolution/deposition of lithium and inhibits lithium dendrite growth, thereby increasing critical current density of the ASSE to 0.65 mA cm−2. An SSLMB assembled with the ASSE and LiFePO4 exhibits excellent performance and cycling stability, maintaining a specific capacity of 125.4 mAh g−1 after 500 cycles at 0.3C.

Large‐Area Ultrathin Metal–Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations

AbstractUltrathin continuous metal–organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic‐imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large‐area fabrication. Here, we propose a ligand back diffusion‐assisted bipolymer‐directed metal ion distribution strategy for preparing large‐area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross‐linked two‐dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large‐area ultrathin MOF membranes. We report the practical fabrication of three representative defect‐free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50–130 nm), including ZIFs and carboxylate‐linker MOFs. Among these, the ZIF‐8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale‐up practicality, MOF membranes were prepared and incorporated into spiral‐wound membrane modules with an active area of 4,800 cm2. The ZIF‐8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).

Large-Area Ultrathin Metal-Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations.

Ultrathin continuous metal-organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic-imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large-area fabrication. Here, we propose a ligand back diffusion-assisted bipolymer-directed metal ion distribution strategy for preparing large-area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross-linked two-dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large-area ultrathin MOF membranes. We report the practical fabrication of three representative defect-free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50-130 nm), including ZIFs and carboxylate-linker MOFs. Among these, the ZIF-8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale-up practicality, MOF membranes were prepared and incorporated into spiral-wound membrane modules with an active area of 4,800 cm2. The ZIF-8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).

Exfoliation of Metal–Organic Frameworks to Give 2D MOF Nanosheets for the Electrocatalytic Oxygen Evolution Reaction

AbstractThe structure and properties of materials are determined by a diverse range of chemical bond formation and breaking mechanisms, which greatly motivates the development of selectively controlling the chemical bonds in order to achieve materials with specific characteristics. Here, an orientational intervening bond‐breaking strategy is demonstrated for synthesizing ultrathin metal–organic framework (MOF) nanosheets through balancing the process of thermal decomposition and liquid nitrogen exfoliation. In such approach, proper thermal treatment can weaken the interlayer bond while maintaining the stability of the intralayer bond in the layered MOFs. And the following liquid nitrogen treatment results in significant deformation and stress in the layered MOFs’ structure due to the instant temperature drop and drastic expansion of liquid N2, leading to the curling, detachment, and separation of the MOF layers. The produced MOF nanosheets with five cycles of treatment are primarily composed of nanosheets that are less than 10 nm in thickness. The MOF nanosheets exhibit enhanced catalytic performance in oxygen evolution reactions owing to the ultrathin thickness without capping agents which provide improved charge transfer efficiency and dense exposed active sites. This strategy underscores the significance of orientational intervention in chemical bonds to engineer innovative materials.

Exfoliation of Metal-Organic Frameworks to Give 2D MOF Nanosheets for the Electrocatalytic Oxygen Evolution Reaction.

The structure and properties of materials are determined by a diverse range of chemical bond formation and breaking mechanisms, which greatly motivates the development of selectively controlling the chemical bonds in order to achieve materials with specific characteristics. Here, an orientational intervening bond-breaking strategy is demonstrated for synthesizing ultrathin metal-organic framework (MOF) nanosheets through balancing the process of thermal decomposition and liquid nitrogen exfoliation. In such approach, proper thermal treatment can weaken the interlayer bond while maintaining the stability of the intralayer bond in the layered MOFs. And the following liquid nitrogen treatment results in significant deformation and stress in the layered MOFs' structure due to the instant temperature drop and drastic expansion of liquid N2, leading to the curling, detachment, and separation of the MOF layers. The produced MOF nanosheets with five cycles of treatment are primarily composed of nanosheets that are less than 10 nm in thickness. The MOF nanosheets exhibit enhanced catalytic performance in oxygen evolution reactions owing to the ultrathin thickness without capping agents which provide improved charge transfer efficiency and dense exposed active sites. This strategy underscores the significance of orientational intervention in chemical bonds to engineer innovative materials.

Two-Dimensional Sulfonate-Functionalized Metal-Organic Framework Membranes for Efficient Lithium-Ion Sieving.

Two-dimensional (2D) membranes have shown promising potential for ion-selective separation but often suffer from the trade-off between permeability and selectivity. Herein, we report an ultrathin 2D sulfonate-functionalized metal-organic framework (MOF) membrane for efficient lithium-ion sieving. The narrow pores with angstrom precision in the MOF assist hydrated ions to partially remove the hydration shell, according to different hydration energies. The abundant sulfonate groups in the MOF channels serve as hopping sites for fast lithium-ion transport, contributing to a high Li-ion permeability. Then, the difference in affinity of the Li+, Na+, K+, and Mg2+ ions to the terminal sulfonate groups further enhances the Li-ion selectivity. The reported ultrathin MOF membrane overcomes the trade-off between permeability and selectivity and opens up a new avenue for highly permselective membranes.

Highly efficient and selective capture of uranium from groundwater by using an ultrathin 2D MOF nanosheet with pocket-like cavities

Highly efficient and selective removal of uranium from aqueous media is crucial for the sustained development of nuclear energy. Herein, we utilized the intrinsic advantages of two-dimensional (2D) metal–organic frameworks (MOFs) and developed an ultrathin 2D MOF nanosheet with cavity structure. The preconcentration of the pocket-like cavities on the MOF nanosheet and sufficient interactions with the adsorption sites in the cavity structure realized highly efficient removal of uranium from water. Even in the low concentration range of 0.05–1 ppm, relatively high removal ratios and fast adsorption kinetics still can be achieved. Additionally, the MOF nanosheet exhibited extremely high anti-interference capability, which can efficiently reduce uranium pollution (0.05–1 ppm) in acid groundwater to the safe level (≤30 ppb) recommended by World Health Organization, and the removal performance was comparable to that in deionized water. The adsorption mechanism was thoroughly studied by Fourier transform infrared analysis, X-ray photoelectron spectroscopy, and density functional theory calculations, which revealed that the interactions between uranyl ions and the carboxylate groups dominated uranium adsorption, and the H-bonding interactions in the pocket-like cavities played an important role in uranium extraction.

Benzothiadiazole-functionalized Zr-MOF nanosheets enable visible-light mediated photocatalytic oxidation of sulfides in water

Ultrathin metal-organic frameworks (MOFs) nanosheets incorporating photochromic units are highly efficient heterogeneous photocatalysts, thanks to their highly exposed catalytic sites, short diffusion pathways, and efficient separation of photo-generated carriers. Herein, we report on the solvothermal synthesis of photoactive benzothiadiazole (BTz) functionalized Zr-MOF nanosheets (Zr-BTDB-NS), which are constructed from Zr12 nodes linked by nine BTDB2− (BTDB = 4,4′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoate) ligands. The Zr-BTDB-NS exhibited superior photocatalytic activity towards the aerobic oxidation of a broad range of sulfides to their corresponding sulfoxides under visible light irradiation in water at room temperature, even in a gram-scale. The Zr-BTDB-NS can be efficiently recycled and reused for seven cycles without a decrease in conversion or selectivity. Detailed mechanism studies revealed that the Zr-BTDB-NS generates singlet oxygen (1O2) and superoxide radical (O2–) reactive oxygen species under visible light irradiation, which are responsible for the oxidation of sulfides into their corresponding sulfoxides. The simplicity of the synthetic approach as well as the diversity of photoactive organic units hold great promise for designing ultrathin, water-stable, and photoactive Zr-MOF nanosheets. This work will also be of added value for selective photooxidation of sulfides under green and mild conditions.

Ultrathin MOF nanosheets and their mixed-matrix membranes for ammonia and aliphatic amine sensing in water.

Ultrathin 2D metal-organic frameworks (MOFs) exhibit a myriad of unparalleled properties, rendering them extensively applicable across various fields. Despite this, developing a 2D MOF sensor for detecting hazardous amines in water remains a formidable challenge. To address this issue, we synthesized Ni-btc MOF ultrathin nanosheets with a thickness of approximately 4.15 nm for the detection of amines in water. These nanosheets demonstrated a notable "turn-on" fluorescence response in the presence of ammonia and aliphatic amines. The detection limit for aliphatic amines ranged from 297 to 424 nM, while for ammonia, it reached an impressive low limit of around 42 nM, which is an excellent value compared to other reported MOFs for ammonia sensing in water. Density functional theory calculations elucidated the mechanism underlying fluorescence enhancement. Additionally, a mixed matrix membrane based on MOF nanosheets was fabricated for real-time sensing that exhibits an immediate color change in the presence of ammonia and aliphatic amines.

Fabrication of Carboxylate-Functionalized 2D MOF Nanosheet with Caged Cavity for Efficient and Selective Extraction of Uranium from Aqueous Solution.

The efficient removal of radioactive uranium from aqueous solution is of great significance for the safe and sustainable development of nuclear power. An ultrathin 2D metal-organic framework (MOF) nanosheet with cavity structures was elaborately fabricated based on a calix[4]arene ligand. Incorporating the permanent cavity structures on MOF nanosheet can fully utilize its structural characteristics of largely exposed surface area and accessible adsorption sites in pollutant removal, achieving ultrafast adsorption kinetics, and the functionalized cavity structure would endow the MOF nanosheets with the ability to achieve preconcentration and extraction of uranium from aqueous solution, affording ultrahigh removal efficiency even in ultra-low concentrations. Thus, more than 97% uranium can be removed from the concentration range of 50-500µgL-1 within 5min. Moreover, the 2D nano-material exhibits ultra-high anti-interference ability, which can efficiently remove uranium from groundwater and seawater. The adsorption mechanism was investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) analysis, and density functional theory (DFT) calculations, which revealed that the cavity structure plays an important role in uranium capture. This study not only realizes highly efficient uranium removal from aqueous solution but also opens the door to achieving ultrathin MOF nanosheets with cavity structures, which will greatly expand the applications of MOF nanosheets.

Ultrathin Metal-Organic Framework Nanosheets for Selective Photocatalytic C2 H2 Semihydrogenation in Aqueous Solution.

The selective semihydrogenation of C2 H2 to C2 H4 in crude C2 H4 (with ~1 vol % C2 H2 contamination) is a crucial process in the manufacture of polyethylene. Comparing to conventional thermalcatalytic route with Pd as catalyst under high temperature with H2 as hydrogen source, photocatalytic C2 H2 reduction reaction with H2 O as hydrogen source can achieve high selectivity under milder conditions, but has rarely been reported. Here, we present a kind of ultrathin metal-organic framework nanosheets (Cu-Co-MNSs) that demonstrate excellent catalytic activities in the semihydrogenation of C2 H2 . Employing Ru(bpy)3 2+ as the photosensitizer, this catalyst attains a noteworthy turnover number (TON) of 2124 for C2 H4 , coupled with an impressive selectivity of 99.5 % after 12 h visible light irradiation. This performance is comparable to molecular catalysts and notably surpasses the efficiency of bulk metal-organic framework materials. Furthermore, Cu-Co-MNSs achieve a 99.95 % conversion of C2 H2 under industrial relevant conditions (1.10 % C2 H2 in C2 H4 ) with 90.3 % selectivity for C2 H4 over C2 H6 , demonstrating a great potential for polymer-grade C2 H4 production.

Step-Nucleation In Situ Self-Repair to Prepare Rollable Large-Area Ultrathin MOF Membranes.

Ultrathin membranes with ultrahigh permeance and good gas selectivity have the potential to greatly decrease separation process costs, but it requires the practical preparation of large area membranes for implementation. Metal-organic frameworks (MOFs) are very attractive for membrane gas separation applications. However, to date, the largest MOF membrane area reported in the literature is only about 100 cm2 . In the present study, a new step-nucleation in situ self-repair strategy is proposed that enables the preparation of large-area (2400 cm2 ) ultrathin and rollable MOF membranes deposited on an inexpensive flexible polymer membrane support layer for the first time, combining a polyvinyl alcohol (PVA)-metal-ion layer and a pure metal-ion layer. The main role of the pure metal-ion layer is to act as the main nucleation sites for MOF membrane growth, while the PVA-metal-ion layer acts as a slow-release metal-ion source, which supplements MOF crystal nucleation to repair any defects occurring. Membrane modules are necessary components for membrane applications, and spiral-wound modules are among the most common module formats that are widely applied in gas separation. A 4800 cm2 spiral-wound membrane modulewas successfully prepared, demonstrating the practical implementation of large-area MOF membranes.

Scalable and sustainable manufacturing of ultrathin metal–organic framework nanosheets (MONs) for solar cell applications

Metal-organic framework nanosheets (MONs) are an emerging class of 2D materials whose tunable chemistry make them ideal for a wide range of sensing, catalytic, electronics and separation applications. However, creating scalable routes to the synthesis of high quality, ultrathin nanosheets remains challenging and little consideration has been given to the economics of making these materials. Here, we demonstrate a scalable synthesis of zinc-porphyrin based nanosheets, Zn2(H2TCPP), for use in organic solar cells and conduct a techno-economic analysis of their pilot-plant scale manufacture. A thorough investigation of the process chemistry of the solvothermal synthesis enabled reduction of reaction time, increased solid content and scale-up of the reaction in batch. Significantly, the addition of triethylamine accelerated the reaction kinetics, which enabled the synthesis temperature to be dropped from > 80 °C to room temperature. Application of these new reaction conditions in a continuous stirred-tank reactor directly formed monolayer MONs at 99 % yield with a space–time yield of 16 kg m−3 day−1, an approximately 20-fold increase in yield compared to adapting the literature procedure. Techno-economic analysis showed a 94 % reduction in the production costs compared to the literature reaction conditions and indicated that the production cost was dominated by ligand price. The general applicability of the method was demonstrated through synthesis of related Cu2(H2TCPP) MONs and tunability through metalation of the porphyrin units with six different metal ions. Finally, the value of the nanosheets was demonstrated through a near doubling in the power conversion efficiency of organic photovoltaic devices when the MONs were incorporated into the active layer. Overall, this work demonstrates the first scalable and sustainable route to producing monolayer nanosheets for high value applications.