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The reaction kinetics of photocatalytic CO2 reduction is highly dependent on the transfer rate of electrons and protons to the CO2 molecules adsorbed on catalytic centers. Studies on uncovering the proton effect in catalysts on photocatalytic activity of CO2 reduction are significant but rarely reported. In this paper, we, from the molecular level, revealed that the photocatalytic activity of CO2 reduction is closely related to the proton availability in catalysts. Specifically, four dinuclear Co(II) complexes based on Robson-type ligands with different number of carboxylic groups (-nCOOH; n = 0, 2, 4, 6) were designed and synthesized. All these complexes show photocatalytic activity for CO2 reduction to CO in a water-containing system upon visible-light illumination. Interestingly, the CO yields increase positively with the increase of the carboxylic-group number in dinuclear Co(II) complexes. The one containing -6COOH shows the best photocatalytic activity for CO2 reduction to CO, with the TON value reaching as high as 10,294. The value is 1.8, 3.4, and 7.8 times higher than those containing -4COOH, -2COOH, and -0COOH, respectively. The high TON value also makes the dinuclear Co(II) complex with -6COOH outstanding among reported homogeneous molecular catalysts for photocatalytic CO2 reduction. Control experiments and density functional theory calculation indicated that more carboxylic groups in the catalyst endow the catalyst with more proton relays, thus accelerating the proton transfer and boosting the photocatalytic CO2 reduction. This study, at a molecular level, elucidates that more carboxylic groups in catalysts are beneficial for boosting the reaction kinetics of photocatalytic CO2 reduction.
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Rational construction of broadband and strong visible-light-absorbing (BSVLA) earth-abundant complexes is of great importance for efficient and sustainable solar energy utilization. Herein, we explore a universal Cu(I) center to couple with multiple strong visible-light-absorbing antennas to break the energy level limitations of the current noble-metal complexes, resulting in the BSVLA nonprecious complex (Cu-3). Systematic investigations demonstrate that double "ping-pong" energy-transfer processes in Cu-3 involving resonance energy transfer and Dexter mechanism enable a BSVLA between 430 and 620 nm and an antenna-localized long-lived triplet state for efficient intermolecular electron/energy transfer. Impressively, Cu-3 exhibited an outstanding performance for both energy- and electron-transfer reactions. Pseudo-first-order rate constant of photooxidation of 1,5-dihydroxynaphthalene with Cu-3 can achieve a record value of 190.8 × 10-3 min-1 among the molecular catalytic systems, over 30 times higher than that with a noble-metal photosensitizer (PS) [Ru(bpy)3]2+. These findings pave the way to develop BSVLA earth-abundant PSs for boosting photosynthesis.
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Complejos de Coordinación , Luz , Fotosíntesis , Fármacos Fotosensibilizantes , Transferencia de EnergíaRESUMEN
SignificanceThe photosensitizer is one of the important components in the photocatalytic system. Molecular photosensitizers have well-defined structures, which is beneficial in revealing the catalysis mechanism and helpful for further structural design and performance optimization. However, separation and recycling of the molecular photosensitizers is a great problem. Loading them into/on two/three-dimensional supports through covalent bonds, electrostatic interactions, and supramolecular interactions is a method that enhances their separation and recycling capability. Nonetheless, the structures of the resulting composites are unclear. Thus, the development of highly crystalline heterogeneity methods for molecular photosensitizers, albeit greatly challenging, is meaningful and desirable in photocatalysis, through which heterogeneous photosensitizers with well-defined structures, definite catalysis mechanisms, and good catalytic performance would be expected.
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Fármacos Fotosensibilizantes , Catálisis , Estructura Molecular , Fármacos Fotosensibilizantes/químicaRESUMEN
Owing to the electrical conductivity and periodic porosity, conductive metal-organic framework (cMOF) ultrathin films open new perspectives to photocatalysis. The space-selective assembly of catalytic sites and photosensitizers in/on cMOF is favorable for promoting the separation of photogenerated carriers and mass transfer. However, the controllable integration of functional units into the cMOF film is rarely reported. Herein, via the synergistic effect of steric hindrance and an electrostatic-driven strategy, the dinuclear-metal molecular catalysts (DMC) and perovskite (PVK) quantum dot photosensitizers were immobilized into channels and onto the surface of cMOF ultrathin films, respectively, affording [DMC@cMOF]-PVK film photocatalysts. In this unique heterostructure, cMOF not only facilitated the charge transfer from PVK to DMC but also guaranteed mass transfer. Using H2O as an electron donor, [DMC@cMOF]-PVK realized a 133.36 µmol·g-1·h-1 CO yield in photocatalytic CO2 reduction, much higher than PVK and DMC-PVK. Owing to the excellent light transmission of films, multilayers of [DMC@cMOF]-PVK were integrated to increase the CO yield per unit area, and the 10-layer device realized a 1115.92 µmol·m-2 CO yield in 4 h, which was 8-fold higher than that of powder counterpart. This work not only lightens the development of cMOF-based composite films but also paves a novel avenue for an ultrathin film photocatalyst.
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ConspectusSolar-driven CO2 reduction into value-added chemicals, such as CO, HCOOH, CH4, and C2+ products, has been regarded as a potential way to alleviate environmental pollution and the energy crisis. In the past decades, numerous pioneered homogeneous catalytic systems composed of soluble photosensitizers (PSs) and catalytic active sites (CASs) have been explored for CO2 photoreduction. Nevertheless, inefficient electron migration based on random collision between CASs and PSs in homogeneous catalytic systems usually causes mediocre performance. Moreover, the relatively poor separation/recycling capability of the homogeneous systems has inevitably reduced their reusability and practicality. The rational combination of PSs and CASs have been proven to play critical roles in the development of highly efficient heterogeneous catalysts to improve their performance, such as anchoring them onto the solid matrixes or connecting them through bridging ligands. However, developing effective assembly strategies to achieve the ordered orientation and uniform heterogenization of PSs and CASs remains a great challenge, mainly due to the lack of crystallinity heterogeneous transformation and structural tailoring ability of traditional solid catalysts. Moreover, due to the lack of assembly and synthesis strategies, many efficient homogeneous photocatalytic systems are still unable to achieve high crystallinity heterogeneous transformation.Metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) have recently attracted broad interest toward CO2 photocatalysis because of their diverse precursors, well-defined and tailorable structures, abundant exposed CASs and high surface areas, etc. Especially, the highly ordered orientation and uniform combination of PSs and CASs in MOFs and COFs are beneficial for improved light harvesting and charge separation, greatly helping to address the aforementioned challenges. Moreover, the well-defined crystalline structures of MOFs and COFs facilitate the establishment of the structure-activity relationship. Therefore, it is increasingly important to summarize the integration of PSs and catalysts to provide deep insight into MOF/COF-based photocatalysts.In this Account, we summarize the ordered integration of PSs and CASs in MOFs and COFs for CO2 photoconversion and describe the structure-activity relationships to guide the design of effective catalysts. Given the unique structural features of MOFs and COFs, we have emphasized the integration of PSs and CASs to optimize their photocatalytic performance, including the confinement of catalytic active nanoparticles (NPs) into photosensitizing frameworks, co-coordination of PSs and CASs, and ligand-to-metal charge-transfer and anchoring CASs on the secondary building units of the photosensitizing frameworks. The catalytic activity, selectivity, sacrificial agent, and stability of these systems were then discussed. More importantly, MOFs and COFs provide powerful platforms to understand the key steps for boosting CO2 photoreduction and exploring the catalytic mechanism, involving light harvesting, electron-hole separation/migration, and surface redox reactions. Finally, the perspective and challenge of CO2 photoreduction in MOF/COF platforms are further proposed and discussed. It is expected that this Account would provide deep insight into the integration of PSs and catalysts in COFs and MOFs with well-defined structures and afford significant inspiration toward enhanced performance in heterogeneous catalysis.
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Homonuclear dual-atomic catalysts showcase unique electronic modulation due to their dual metal centres, providing new direction in development of efficient catalysts for CO2 electroreduction. This article highlights a few cutting-edge homonuclear dual-atomic catalysts, focusing on their inherent advantages in efficient and selective CO2 electroreduction, to spotlight the potential application of dual-atomic catalysts in CO2 electroreduction.
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The development of low-cost and efficient photocatalysts to achieve water splitting to hydrogen (H2) is highly desirable but remains challenging. Herein, we design and synthesize two porous polymers (Co-Salen-P and Fe-Salen-P) by covalent bonding of salen metal complexes and pyrene chromophores for photocatalytic H2 evolution. The catalytic results demonstrate that the two polymers exhibit excellent catalytic performance for H2 generation in the absence of additional noble-metal photosensitizers and cocatalysts. Particularly, the H2 generation rate of Co-Salen-P reaches as high as 542.5 µmol g-1 h-1, which is not only 6 times higher than that of Fe-Salen-P but also higher than a large amount of reported Pt-assisted photocatalytic systems. Systematic studies show that Co-Salen-P displays faster charge separation and transfer efficiencies, thereby accounting for the significantly improved photocatalytic activity. This study provides a facile and efficient way to fabricate high-performance photocatalysts for H2 production.
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Catalysts featuring dinuclear metal sites are regarded as superior systems compared with their counterparts with mononuclear metal sites. The dinuclear metal sites in catalysts with appropriate spatial separations and geometric configurations can confer the dinuclear metal synergistic catalysis (DMSC) effect, and thus boost the catalytic performance, in particular for reactions involving multiple reactants, intermediates and products. In this review, we summarize the related reports on the design and synthesis of both homogeneous and heterogeneous dinuclear metal catalysts, and their applications in energy conversion reactions, including photo-/electro-catalytic hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), CO2 reduction reaction (CO2RR), and N2 reduction reaction (N2RR). Particularly, we focus on the analysis of the relationship between the catalyst structure and catalytic performances, where the design principles are presented. Finally, we discuss the challenges in the design and preparation of dinuclear metal catalysts with the DMSC effect and present a perspective on the future development of dinuclear metal catalysts in energy conversion. This review aims to comprehensively summarize the up-to-date research progress on the synthesis and energy-related application of dinuclear metal catalysts and provide guidance for designing energy-conversion catalysts with superior performances.
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Solar-driven CO2 reduction and water oxidation to liquid fuels represents a promising solution to alleviate energy crisis and climate issue, but it remains a great challenge for generating CH3OH and CH3CH2OH dominated by multi-electron transfer. Single-cluster catalysts with super electron acceptance, accurate molecular structure, customizable electronic structure and multiple adsorption sites, have led to greater potential in catalyzing various challenging reactions. However, accurately controlling the number and arrangement of clusters on functional supports still faces great challenge. Herein, we develop a facile electrosynthesis method to uniformly disperse Wells-Dawson- and Keggin-type polyoxometalates on TiO2 nanotube arrays, resulting in a series of single-cluster functionalized catalysts P2M18O62@TiO2 and PM12O40@TiO2 (M=Mo or W). The single polyoxometalate cluster can be distinctly identified and serves as electronic sponge to accept electrons from excited TiO2 for enhancing surface-hole concentration and promote water oxidation. Among these samples, P2Mo18O62@TiO2-1 exhibits the highest electron consumption rate of 1260â µmol g-1 for CO2-to-CH3OH conversion with H2O as the electron source, which is 11â times higher than that of isolated TiO2 nanotube arrays. This work supplied a simple synthesis method to realize the single-dispersion of molecular cluster to enrich surface-reaching holes on TiO2, thereby facilitating water oxidation and CO2 reduction.
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The sensitizing ability of a catalytic system is closely related to the visible-light absorption ability, excited-state lifetime, redox potential, and electron-transfer rate of photosensitizers (PSs), however it remains a great challenge to concurrently mediate these factors to boost CO2 photoreduction. Herein, a series of Ir(III)-based PSs (Ir-1-Ir-6) were prepared as molecular platforms to understand the interplay of these factors and identify the primary factors for efficient CO2 photoreduction. Among them, less efficient visible-light absorption capacity results in lower CO yields of Ir-1, Ir-2 or Ir-4. Ir-3 shows the most efficient photocatalytic activity among these mononuclear PSs due to some comprehensive parameters. Although the Kobs of Ir-3 is ≈10â times higher than that of Ir-5, the CO yield of Ir-3 is slightly higher than that of Ir-5 due to the compensation of Ir-5's strong visible-light-absorbing ability. Ir-6 exhibits excellent photocatalytic performance due to the strong visible-light absorption ability, comparable thermodynamic driving force, and electron transfer rate among these PSs. Remarkably, the CO2 photoreduction to CO with Ir-6 can achieve 91.5â µmol, over 54â times higher than Ir-1, and the optimized TONC-1 can reach up to 28160. Various photophysical properties of the PSs were concurrently adjusted by fine ligand modification to promote CO2 photoreduction.
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Covalent organic frameworks (COFs) have been widely studied in photocatalytic CO2 reduction reaction (CO2 RR). However, pristine COFs usually exhibit low catalytic efficiency owing to the fast recombination of photogenerated electrons and holes. In this study, we fabricated a stable COF-based composite (GO-COF-366-Co) by covalently anchoring COF-366-Co on the surface of graphene oxide (GO) for the photocatalytic CO2 reduction. Interestingly, in absolute acetonitrile (CH3 CN), GO-COF-366-Co shows a high selectivity of 94.4 % for the photoreduction of CO2 to formate, with a formate yield of 15.8â mmol/g, which is approximately four times higher than that using the pristine COF-366-Co. By contrast, in CH3 CN/H2 O (v : v=4 : 1), the main product for the photocatalytic CO2 reduction over GO-COF-366-Co is CO (96.1 %), with a CO yield as high as 52.2â mmol/g, which is also approximately four times higher than that using the pristine COF-366-Co. Photoelectrochemical experiments demonstrate the covalent bonding of COF-366-Co and GO to form the GO-COF-366-Co composite facilitates charge separation and transfer significantly, thereby accounting for the enhanced catalytic activity. In addition, theoretical calculations and in situ Fourier transform infrared spectroscopy reveal H2 O can stabilize the *COOH intermediate to further form a *CO intermediate via O-H(aq)â â â O(*COOH) hydrogen bonding, thus explaining the regulated photocatalytic performance.
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The construction of secondary building units (SBUs) in versatile metal-organic frameworks (MOFs) represents a promising method for developing multi-functional materials, especially for improving their sensitizing ability. Herein, we developed a dual small molecules auxiliary strategy to construct a high-nuclear transition-metal-based UiO-architecture Co16-MOF-BDC with visible-light-absorbing capacity. Remarkably, the N3 - molecule in hexadecameric cobalt azide SBU offers novel modification sites to precise bonding of strong visible-light-absorbing chromophores via click reaction. The resulting Bodipy@Co16-MOF-BDC exhibits extremely high performance for oxidative coupling benzylamine (~100 % yield) via both energy and electron transfer processes, which is much superior to that of Co16-MOF-BDC (31.5 %) and Carboxyl @Co16-MOF-BDC (37.5 %). Systematic investigations reveal that the advantages of Bodipy@Co16-MOF-BDC in dual light-absorbing channels, robust bonding between Bodipy/Co16 clusters and efficient electron-hole separation can greatly boost photosynthesis. This work provides an ideal molecular platform for synergy between photosensitizing MOFs and chromophores by constructing high-nuclear transition-metal-based SBUs with surface-modifiable small molecules.
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Dinuclear metal synergistic catalysis (DMSC) has been proved an effective approach to enhance catalytic efficiency in photocatalytic CO2 reduction reaction, while it remains challenge to design dinuclear metal complexes that can show DMSC effect. The main reason is that the influence of the microenvironment around dinuclear metal centres on catalytic activity has not been well recognized and revealed. Herein, we report a dinuclear cobalt complex featuring a planar structure, which displays outstanding catalytic efficiency for photochemical CO2-to-CO conversion. The turnover number (TON) and turnover frequency (TOF) values reach as high as 14457 and 0.40â s-1 respectively, 8.6â times higher than those of the corresponding mononuclear cobalt complex. Control experiments and theoretical calculations revealed that the enhanced catalytic efficiency of the dinuclear cobalt complex is due to the indirect DMSC effect between two CoII ions, energetically feasible one step two-electron transfer process by Co2 I,I intermediate to afford Co2 II,II(CO2 2-) intermediate and fast mass transfer closely related with the planar structure.
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In proton exchange membrane water electrolysis (PEMWE), the anode oxygen evolution reaction (OER) catalysts rely heavily on the expensive and scarce iridium-based materials. Ruthenium dioxide (RuO2) with lower price and higher OER activity, has been explored for the similar task, but has been restricted by the poor stability. Herein, we developed an anion modification strategy to improve the OER performance of RuO2 in acidic media. The designed multicomponent catalyst based on sulfate anchored on RuO2/MoO3 displays a low overpotential of 190 mV at 10 mA cm-2 and stably operates for 500 hours with a very low degradation rate of 20 µV h-1. When assembled in a PEMWE cell, this catalyst as an anode shows an excellent stability at 500 mA cm-2 for 150 h. Experimental and theoretical results revealed that MoO3 could stabilize sulfate anion on RuO2 surface to suppress its leaching during OER. Such MoO3-anchored sulfate not only reduces the formation energy of *OOH intermediate on RuO2, but also impedes both the surface Ru and lattice oxygen loss, thereby achieving the high OER activity and exceptional durability.
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The development of high-performance photocatalytic systems for CO2 reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs2AgBiBr6 nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13â µmol g-1 h-1 for visible-light-driven CO2-to-CO conversion coupled with water oxidation to O2, over 8â times of the unmodified Cs2AgBiBr6 (36±8â µmol g-1 h-1), also far surpassing the documented systems (<150â µmol g-1 h-1). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs2AgBiBr6 can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis.
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Hydrogen-bonded organic frameworks (HOFs) are outstanding candidates for photocatalytic hydrogen evolution. However, most of reported HOFs suffer from poor stability and photocatalytic activity in the absence of Pt cocatalyst. Herein, a series of metal HOFs (Co2-HOF-X, X=COOMe, Br, tBu and OMe) have been rationally constructed based on dinuclear cobalt complexes, which exhibit exceptional stability in the presence of strong acid (12â M HCl) and strong base (5â M NaOH) for at least 10â days. More impressively, by varying the -X groups of the dinuclear cobalt complexes, the microenvironment of Co2-HOF-X can be modulated, giving rise to obviously different photocatalytic H2 production rates, following the -X group sequence of -COOMe>-Br>-tBu>-OMe. The optimized Co2-HOF-COOMe shows H2 generation rate up to 12.8â mmol g-1 h-1 in the absence of any additional noble-metal photosensitizers and cocatalysts, which is superior to most reported Pt-assisted photocatalytic systems. Experiments and theoretical calculations reveal that the -X groups grafted on Co2-HOF-X possess different electron-withdrawing ability, thus regulating the electronic structures of Co catalytic centres and proton activation barrier for H2 production, and leading to the distinctly different photocatalytic activity.
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Artificial photosynthesis for CO2 reduction coupled with water oxidation currently suffers from low efficiency due to inadequate interfacial charge separation of conventional Z-scheme heterojunctions. Herein, an unprecedented nanoscale Janus Z-scheme heterojunction of CsPbBr3 /TiOx is constructed for photocatalytic CO2 reduction. Benefitting from the short carrier transport distance and direct contact interface, CsPbBr3 /TiOx exhibits significantly accelerated interfacial charge transfer between CsPbBr3 and TiOx (8.90 × 108 s-1 ) compared with CsPbBr3 :TiOx counterpart (4.87 × 107 s-1 ) prepared by traditional electrostatic self-assembling. The electron consumption rate of cobalt doped CsPbBr3 /TiOx can reach as high as 405.2 ± 5.6 µmol g-1 h-1 for photocatalytic CO2 reduction to CO coupled with H2 O oxidation to O2 under AM1.5 sunlight (100 mW cm-2 ), over 11-fold higher than that of CsPbBr3 :TiOx , and surpassing the reported halide-perovskite-based photocatalysts under similar conditions. This work provides a novel strategy to boost charge transfer of photocatalysts for enhancing the performance of artificial photosynthesis.
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This study is designed to compare drug encapsulation by cucurbit[7]uril and ß-cyclodextrin, using fluorofenidone as a model drug. Single-crystal X-ray diffraction analysis was employed to successfully determine the crystal structures of fluorofenidone·H+@cucurbit[7]uril Form, fluorofenidone@cucurbit[7]uril Form, and fluorofenidone@ß-cyclodextrin Form. Keto-enol tautomerization of fluorofenidone mediated by cucurbit[7]uril in acid solution is confirmed by crystal structures, pH titration, and nuclear magnetic resonance experiments. However, ß-cyclodextrin cannot cause the keto-enol tautomerization of fluorofenidone under similar conditions. The phase solubility study demonstrates that cucurbit[7]uril has a much higher solubilization capacity for fluorofenidone than ß-cyclodextrin in 0.1 M HCl since the Kc values of fluorofenidone with cucurbit[7]uril and ß-cyclodextrin were 1223.97 ± 452.68 and 78.49 ± 10.56 M-1, respectively. Excellent solubility can be attributed to the keto-enol tautomerization of fluorofenidone under the conditions of cucurbit[7]uril in acid solution. The enol form of fluorofenidone is encapsulated by cucurbit[7]uril by hydrogen bonding interaction and hydrophobic interaction to increase binding affinity. Rat pharmacokinetic studies demonstrate that the area under the plasma concentration-time curve from time 0 to 7 h value of fluorofenidone@cucurbit[7]uril complex is 1.70-fold greater than that of free fluorofenidone, and the mean residence time from time 0 to 7 h is slightly prolonged from 1.29 to 1.76 h (P < 0.01) after oral administration. However, no significant difference is found between fluorofenidone and fluorofenidone@ß-cyclodextrin complex. This work indicates that the induction of keto-enol tautomerization of drugs using macrocyclic molecules has the potential to be an effective method to improve their solubility and bioavailability, providing valuable insights for the application of macrocyclic molecules in the biomedical field.
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Compuestos Macrocíclicos , beta-Ciclodextrinas , Ratas , Animales , Solubilidad , beta-Ciclodextrinas/química , Compuestos Macrocíclicos/química , Hidrocarburos Aromáticos con Puentes/químicaRESUMEN
Carbon dioxide cycloaddition into fine chemicals is prospective technology to solve energy crisis and environmental issues. However, high temperature and pressure are usually required in the conventional cycloaddition reactions of CO2 with epoxides. Moreover, metal active sites play a vital role in the CO2 cycloaddition, but it is still unclear. Herein, we select the isostructural MOF-919-Cu-Fe and MOF-919-Cu-Al as models to promote the performance and clarify the effects of metal type on the CO2 cycloaddition. The MOF-919-Cu-Fe with exposed Fe and Cu Lewis acid sites reaches the CO2 cycloaddition with over 99.9% conversion and over 99.9% selectivity at room temperature and a 1 bar CO2 atmosphere, 3.0- and 52.6-fold higher than those of the MOF-919-Cu-Al with Al and Cu sites (33.8%) and the 1H-pyrazole-4-carboxylic acid, Fe, and Cu mixed system (1.9%), respectively. The proposed mechanism demonstrated that the exposed Fe3+ sites facilitate the ring opening of epoxide and CO2 activation to boost the CO2 cycloaddition reaction. This work provides a new insight to tune the catalytic sites of MOFs to achieve high performance for CO2 fixation.
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The development of hierarchically porous metal-organic frameworks (MOFs) with high stability is desirable to expand their applications but remains challenging. Herein, an anionic sodalite-type microporous MOF (Yb-TTCA; TTCA3- = triphenylene-2,6,10-tricarboxylate) was synthesized, which shows outstanding catalytic activities for the cycloaddition of CO2 into cyclic carbonates. Moreover, the microporous Yb-TTCA can be transformed into a hierarchical micro- and mesoporous Yb-TTCA by water treatment with the mesopore sizes of 2 to 12 nm. The hierarchically porous Yb-TTCA (HP-Yb-TTCA) not only exhibits a high thermal stability up to 500 °C but also shows a high chemical stability in aqueous solutions with pH values ranging from 2 to 12. In addition, the HP-Yb-TTCA displays enhanced performance for the removal of organic dyes in comparison with microporous Yb-TTCA. This work provides a facile way to construct hierarchically porous MOF materials.