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The successful development of a photocatalyst/biocatalyst integrated system that carries out selective methanol production from CO2 is reported herein. The fine-tuned system was derived from a judicious combination of graphene-based visible light active photocatalyst (CCG-IP) and sequentially coupled enzymes. The covalent attachment of isatin-porphyrin (IP) chromophore to chemically converted graphene (CCG) afforded newly developed CCG-IP photocatalyst for this research endeavor. The current work represents a new benchmark for carrying out highly selective methanol formation from CO2 in an environmentally benign manner.

The photocatalyst-enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO(2). The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO(2).

Graphical abstract Highlights • Physicochemical properties of graphene oxide modified with cobalt metalated aminoporphyrin. • Photosynthetic conversion of formic acid from carbon-dioxide. • Significantly effective for NADH photoregeneration. • Photoelectrochemical measurement showed photocurrent properties. • Energy applications. Abstract An increasingly level of one of the important greenhouse gas, CO 2 , in the atmosphere from anthropogenic human activities has several adverse consequences and thus, chemical transformation of carbon dioxide into useful, renewable and environmentally friendly products is becoming an important research problem. In the present investigation, we have developed photocatalyst of graphene oxide modified with cobalt metallated aminoporphyrin (GO-Co-ATPP) for conversion of CO 2 to formic acid under visible light. The efficiency of nanohybrid photosynthetic conversion of formic acid from carbon-dioxide is 96.49 μmol for 2 h. We have used XRD, SEM, HR-TEM, AFM, thermogravimetric analysis, BET measurement to establish the structural and physical properties along with infrared spectroscopy and Raman spectroscopy for chemical properties of GO-Co-ATPP. The photocatalyst was significantly effective for NADH photoregeneration with cumulative 48.53% over time and photoelectrochemical measurement showed photocurrent properties. These results strongly suggest that the GO-Co-ATPP photocatalyst materials may open new vistas in conversion of CO 2 into useful and environmentally friendly products as well as energy applications. [ABSTRACT FROM AUTHOR]

• This manuscript focuses on how structural ordering can facilitate the formation of formic at ultra-low potential, which is a critical challenge via photocatalysis. • Human dependency on fossil fuels not only spikes the CO2 levels in the atmosphere but also depletes the limited energy resources. • The photocatalyst-enzyme integrated artificial system emerged as a benchmark for CO2 fixation solving both the energy crisis and carbon emission simultaneously. • Herein a TBE-Y photocatalyst designed by coupling triptycene (T) with eosin-Y (EY) through friedel craft reaction shows excellent solar light harvesting property, high molar extinction coefficient, and appropriate band-gap. • The as-synthesized 3D polymeric TBE-Y photocatalyst exhibits high NADH regeneration (78.77%) which when consecutively coupled with enzyme (formate dehydrogenase) via electron mediator produces HCOOH from CO2 in high yield. Carbon dioxide, one of the primary greenhouse gasses leading to global warming, ocean acidification, and climate change is an obnoxious concern. Human dependency on fossil fuels not only spikes the CO 2 level but also depletes the limited energy resources. The horrendous impact of carbon footprint has made the reduction of CO 2 into solar fuel an indispensable task. The photocatalyst-enzyme integrated artificial system has emerged as a benchmark for CO 2 fixation solving both the energy crisis and carbon emission simultaneously. Herein a TBE-Y photocatalyst designed by coupling triptycene (T) with eosin-Y (EY) through Friedel Craft reaction shows excellent solar light harvesting property, high molar extinction coefficient, and appropriate band-gap. The as-synthesized 3D polymeric TBE-Y photocatalyst exhibits high NADH regeneration (78.77%) which when consecutively coupled with enzyme (formate dehydrogenase) via electron mediator produces HCOOH (189.34 μmol) from CO 2 in high yield in 2 h. The graphical abstract shows the formation and regeneration of HCOOH from CO 2 and NADH respectively through TBE-Y photocatalyst under solar light irradiation. The TBE-Y photocatalyst was formed through Friedel craft reaction by the coupling of Triptycene and Eosin-Y, which is utilized for HCOOH formation from CO 2 in the presence of Solar light. Formic acid and NADH regeneration have a wide application in pharmaceutical companies. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: The conversion of CO2 to valuable solar fuels by means of solar energy using metal‐free flexible film photocatalysts is an appealing strategy. Here we demonstrate a three dimensional aromatic polymer (3DAP) derived from triptycene (TC) as a metal free, stable and highly efficient visible light responsive flexible film photocatalyst for selective solar fuel production from CO2. For this research work, the polymerization of TC by the Diels–Alder reaction is exploited for the first time as a new synthetic approach for the construction of three dimensional aromatic polymer photocatalyst. The visible‐light harvesting ability, band gap suitability, high Brunauer–Emmett–Teller (BET) surface area and electron transfer capability via interconnecting 3D chain of 3DAP contribute to the excellent performance of the film photocatalyst as evident from 91.09 % NADH regeneration and 225.12 μmol of formic acid production. This work provides important insights into the design of flexible polymer film photocatalyst for selective solar fuel formation from CO2 and is expected to trigger further interest in sustainable solar energy conversion applications such as tailorable and wearable devices. [ABSTRACT FROM AUTHOR]

Abstract: The conversion of CO2 to valuable solar fuels by means of solar energy using metal‐free flexible film photocatalysts is an appealing strategy. Here we demonstrate a three dimensional aromatic polymer (3DAP) derived from triptycene (TC) as a metal free, stable and highly efficient visible light responsive flexible film photocatalyst for selective solar fuel production from CO2. For this research work, the polymerization of TC by the Diels–Alder reaction is exploited for the first time as a new synthetic approach for the construction of three dimensional aromatic polymer photocatalyst. The visible‐light harvesting ability, band gap suitability, high Brunauer–Emmett–Teller (BET) surface area and electron transfer capability via interconnecting 3D chain of 3DAP contribute to the excellent performance of the film photocatalyst as evident from 91.09 % NADH regeneration and 225.12 μmol of formic acid production. This work provides important insights into the design of flexible polymer film photocatalyst for selective solar fuel formation from CO2 and is expected to trigger further interest in sustainable solar energy conversion applications such as tailorable and wearable devices. [ABSTRACT FROM AUTHOR]

[Display omitted] • Artificial photosynthesis. • Easy to make polydopamine modified sulphur doped GCN photocatalyst for generation of HCOOH from CO 2. • P@SGCN photocatalyst utilizes in the artificial photosynthetic system for the highly selective generation of formic acid from CO 2 under sun ray irradiation. The photocatalytic transformations of CO 2 into solar chemicals are a promising way in views of green energy and environmental sustainability. Improving the low catalytic performance and poor selectivity of the photocatalysts are one of the great challenges in this field. By mimicking the natural photosynthesis and taking advantage of the enzyme's high specificity and efficiency, we designed the metal-free photocatalyst combined to an enzyme in order to synergistically solve the stated problems. In this work, we developed a metal-free polydopamine (P) modified sulfur-doped graphitic carbon nitride (P@SGCN) photocatalyst for the regeneration of NADH and the highly selective production of formic acid, HCOOH, from CO 2. Our study shows a new way for the applications of polydopamine-modified photocatalysts to produce the solar chemicals/fuels from CO 2. [ABSTRACT FROM AUTHOR]

A spherical photocatalyst to emulate natural photosynthesis for the production of formic acid from CO 2. [Display omitted] • Efficient photocatalytic formic acid production from CO 2 has been carried out by a novel Bromophenol-Bakelite (BPB) composite. • The as prepared photocatalyst was characterized by several characterization techniques to determine the physio-chemical properties. • The prepared photocatalyst is found to be visible light active and was further used for the regeneration of NADH and formation of formic acid. • The yield for solar light driven NADH regeneration and formic acid production by this photocatalyst was found to be 82.52 % and 220 μmol respectively. The conversion of carbon dioxide (CO 2) to various chemical compounds is an attractive solution to overcome the global energy and environmental crisis. However, the chemical stability of CO 2 hinders the many chemical applications such as photochemical conversion processes. In this work, we developed the efficient photocatalytic reactions for the production of formic acid from CO 2 and the NADH regeneration by employing a novel Bromophenol-Bakelite (BPB) composite. We synthesized the BPB photocatalyst with the bromophenol blue dye-doped inside the Bakelite matrix. The BPB-composite showed the excellent photocatalytic abilities combined to the photocatalyst − enzyme coupled artificial photosynthetic system. For the production of formic acid and the NADH regeneration, the catalytic efficiencies of BPB-composite were much higher than those of bromophenol. Our approach will open up the new way toward the selective productions of solar chemicals directly converted from CO 2 via the artificial photosynthesis. [ABSTRACT FROM AUTHOR]

The consumption of carbon dioxide (CO 2) for direct solar fuel productions and synthesis of fine solar chemicals are gaining leading significance due to the shortage of fossil-fuel and global warming worldwide. Therefore, herein, we report the synthesis and development of solar light harvesting bamboo - shape magnesium tetraphenyl porphyrin based framework (Mg-TPPBF) photocatalyst. The development of Mg-TPPBF photocatalyst-biocatalyst bonded system as a solar light harvesting photocatalyst functions in a extremely efficient manner, increasing to high regeneration of NADH (73.9%), followed by its utilization in exclusive amount of formic acid (HCOOH) production (197.2 μmol) from CO 2. The Mg-TPPBF photocatalyst also enables in consecutive C-S/C-N bonds formation with high yield (~96–99%) and selectivity (~97–99%) under solar light with excellent reusability. The current research work highlights the enlargement and application of Mg-TPPBF photocatalyst for direct solar fuel production from CO 2 and fine solar chemical synthesis. • Atmospheric CO 2 level enhancement cause serious environmental problems. • Mg-TPPBF−F ate DH coupled artificial photosynthetic system reduces CO 2 into HCOOH. • Mg-TPPBF photocatalyst catalyzed C-S/C-N bonds formation under solar light. • The photocatalytic products are useful in agrochemical & pharmacological actions. [ABSTRACT FROM AUTHOR]

The photocatalyst-enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO2. The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO2. [ABSTRACT FROM AUTHOR]

Abstract: The front cover artwork for issue 9/2018 is provided by Prof. Jin‐Ook Baeg's artificial photosynthesis research group from Korea Research Institute of Chemical Technology (KRICT), Republic of Korea. The image shows a light harvesting 3D aromatic polymer (3DAP) derived from triptycene that can efficiently and selectively convert CO2 to formic acid. See the Full Paper itself at https://doi.org/10.1002/cctc.201701730. [ABSTRACT FROM AUTHOR]

Abstract: The front cover artwork for issue 9/2018 is provided by Prof. Jin‐Ook Baeg's artificial photosynthesis research group from Korea Research Institute of Chemical Technology (KRICT), Republic of Korea. The image shows a light harvesting 3D aromatic polymer (3DAP) derived from triptycene that can efficiently and selectively convert CO2 to formic acid. See the Full Paper itself at https://doi.org/10.1002/cctc.201701730. [ABSTRACT FROM AUTHOR]