CO 2 activation and conversion by enzymes to produce value-added multi-carbon compounds under mild conditions show significant impact on carbon neutrality. However, the enzyme co-factor NADH is expensive and the regeneration is still challenging for the enzyme reaction process. Inspired by natural photosynthesis, this study successfully developed a biomimetic photocatalyst Ce/TCPP-UiO-66-NH 2 (TCPP: meso-tetrakis (4-carboxyphenyl) porphine) for NADH regeneration and CO 2 activation. Structure analysis and spectra showed that the co-doping of Ce and TCPP reduced the band gap width of UiO-66-NH 2 , improved the separation efficiency of photo-generated carriers, and endowed it with excellent photocatalytic performance. The synthesized biomimetic photocatalyst Ce/TCPP-UiO-66-NH 2 was then applied for NADH regeneration. The regeneration efficiency of NADH can reach up to 95 % after 3 h of light reaction, which was about 1.6 times higher than that of the control group. Ultra-fast femtosecond time-resolved transient absorption (fs-TA) showed that Ce/TCPP-UiO-66-NH 2 possessed the shortest average decay time ( τ ¯ = 1.12 ps), indicating shorter average life-time of carriers after Ce doping, thus suppressing hole-electron recombination. Finally, the key enzyme formate dehydrogenase (FDHPa) for CO 2 activation was immobilized on the membrane, combining with light regeneration of NADH for CO 2 production to formate. The formate yield (3.1 mM) was 16 times higher than that of the control group (0.19 mM). This work provided an effective strategy and efficient photocatalyst for the biomimetic photocatalytic activation of CO 2 to formate, which is an indispensable bridge for the further high-valuable C n compounds production by biocatalysis.
Jiaqian Zhang,Jinjuan Xue,Zhenbo Wu,Mingxin Wang,Yiting Lv,Zhaoxia Chen,Shuaishuai Ma
In this work, we fabricated a multifunctional membrane by in-situ growth of tetrakis (4-carboxyphenyl) porphyrin-doped UiO-66-NH 2 on stainless steel mesh (SSM), denoted as TCPP/UiO@SSM, for gravity-driven oil–water/seawater mixtures separation and visible-light-driven bacterial inactivation. The as-prepared membrane exhibited high permeation flux (up to 46312 ± 1583 L m −2 h −1 ) as well as separation efficiency (above 98%) towards various oil–water/seawater mixtures separation, which resulted from the rough hierarchical structure and the inherent super-wettability. In particular, the membrane can effectively deal with viscous oil fouling to achieve a desired flux recovery ratio (FRR) after separating crude oil from water, attributing to the self-cleaning property originated from the photo-active TCPP/UiO. Furthermore, the as-fabricated TCPP/UiO@SSM has the ability to efficiently inactivate typical Gram bacteria (6 log units) in water under visible light . Both the oil–water separation and photocatalytic sterilization performances of TCPP/UiO@SSM are superior to UiO@SSM. The doping of photosensitive TCPP in UiO-66-NH 2 not only improved the hydrophilicity, but also enhanced the photocatalytic activity by creating a Z-scheme heterojunction to promote the separation of charge carriers and amplify the photothermal effect. This work provides a new platform for water disinfection and the treatment of oily wastewater containing viscous oil phase based on UiO metal–organic framework.
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