Acid and Base Resistant Zirconium Polyphenolate‐Metalloporphyrin Scaffolds for Efficient CO₂ Photoreduction

Abstract

A series of zirconium polyphenolate-decorated-(metallo)porphyrin metal-organic frameworks (MOFs), ZrPP-n (n = 1, 2), featuring infinite Zr -oxo chains linked via polyphenolate groups on four peripheries of eclipse-arranged porphyrin macrocycles, are successfully constructed through a top-down process from simulation to synthesis. These are the unusual examples of Zr-MOFs (or MOFs in general) based on phenolic porphyrins, instead of commonly known carboxylate-based types. Representative ZrPP-1 not only exhibits strong acid resistance (pH = 1, HCl) but also remains intact even when immersed in saturated NaOH solution (≈20 m), an exceptionally large range of pH resistance among MOFs. The metallation at the porphyrin core gives rise to materials with enhanced sorption and catalytic properties. In particular, ZrPP-1-Co, with precise and uniform distribution of active centers, exhibits not only high CO trapping capability (≈90 cm g at 1 atm, 273 K, among the highest in Zr-MOFs) but also high photocatalytic activity for reduction of CO into CO (≈14 mmol g h ) and high selectivity over CH (>96.4%) without any cocatalyst under visible-light irradiation (λ > 420 nm). Given the strong chemical resistance under extreme alkali conditions, these catalysts can be recycled without appreciable loss of activity. The possible mechanism for photocatalytic reduction of CO -to-CO over ZrPP-1-Co is also proposed.

Encapsulating a Ni(II) molecular catalyst in photoactive metal–organic framework for highly efficient photoreduction of CO2

“…As shown in Fig. 4a, the generation of CO increases almost linearly with irradiation time upon 10 h. Ni3@Ru-UiO-67 exhibits the CO evolution rate of 426.05 mmol/(g h) (85.21 mmol) with a catalytic turnover number (TON) of 510.0 (defined as n(CO)/n(Ni(bpet)(H 2 O) 2 ), which holds a high catalytic performance among reported MOF catalysts (Table S4 online) [38,39]. Notably, only a negligible amount of H 2 could be detected (Fig.…”

Design of Single‐Site Photocatalysts by Using Metal–Organic Frameworks as a Matrix

“…More recently,aseries of Zr-based MOFs (ZrPP-1-M) were synthesized by using THPP-M (THPP = 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl);M = H 2 ,Z n, Cu, Fe, Co) as the organic linker and applied for CO 2 conversion under visible-light irradiation. [37] Of theseM OFs, ZrPP-1-Co displayed high CO 2 adsorption capacitya nd high stabilityo ver al arge pH range, and remarkable photocatalytic activity towards CO 2 reduction.…”

“…The electronic structure of the porphyrin macrocycle was significantly changed by the metalation of In III and Sn IV , which resulted in high photostability and efficient photocatalytic performance in the aerobic hydroxylation of arylboronic acids, amine coupling, and the Mannich reaction. More recently, a series of Zr‐based MOFs (ZrPP‐1‐M) were synthesized by using THPP‐M (THPP=5,10,15,20‐tetrakis(3,4,5‐trihydroxyphenyl); M=H 2 , Zn, Cu, Fe, Co) as the organic linker and applied for CO 2 conversion under visible‐light irradiation . Of these MOFs, ZrPP‐1‐Co displayed high CO 2 adsorption capacity and high stability over a large pH range, and remarkable photocatalytic activity towards CO 2 reduction.…”

Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction

“…Moreover, in 2018, Chen et al discovered a Zr-based MOF with extraordinarily great pH resilience (hyperstability of all Zr-MOFs) to harsh (HCl, pH = 1 and concentrated NaOH) reaction condition [139]. Via a top-down synthesis process, MOFs (Zr 2 C 44 H 22 O 12 N 4 (ZrPP-1)) with NbO-like topology, featuring immense Zr(IV)-oxo chains linked by polyphenolate groups on four peripheries of eclipse-organized porphyrin macrocycles, were successfully constructed by deploying non-intercrossed Zr(IV)-pyrogallic porphyrin MOFs, ZrPP-1.…”