Ancient Loss of Catalytic Selenocysteine Spurred Convergent Adaptation in a Mammalian Oxidoreductase.

Selenocysteine, the 21st amino acid specified by the genetic code, is a rare selenium-containing residue found in the catalytic site of selenoprotein oxidoreductases. Selenocysteine is analogous to the common cysteine amino acid, but its selenium atom offers physical-chemical properties not provided by the corresponding sulfur atom in cysteine. Catalytic sites with selenocysteine in selenoproteins of vertebrates are under strong purifying selection, but one enzyme, glutathione peroxidase 6 (GPX6), independently exchanged selenocysteine for cysteine <100 million years ago in several mammalian lineages. We reconstructed and assayed these ancient enzymes before and after selenocysteine was lost and up to today and found them to have lost their classic ability to reduce hydroperoxides using glutathione. This loss of function, however, was accompanied by additional amino acid changes in the catalytic domain, with protein sites concertedly changing under positive selection across distant lineages abandoning selenocysteine in glutathione peroxidase 6. This demonstrates a narrow evolutionary range in maintaining fitness when sulfur in cysteine impairs the catalytic activity of this protein, with pleiotropy and epistasis likely driving the observed convergent evolution. We propose that the mutations shared across distinct lineages may trigger enzymatic properties beyond those in classic glutathione peroxidases, rather than simply recovering catalytic rate. These findings are an unusual example of adaptive convergence across mammalian selenoproteins, with the evolutionary signatures possibly representing the evolution of novel oxidoreductase functions.

Photothermal Conversion Porous Organic Polymers: Design, Synthesis, and Applications.

Solar energy is a primary form of renewable energy, and photothermal conversion is a direct conversion process with tunable conversion efficiency. Among various kinds of photothermal conversion materials, porous organic polymers (POP) are widely investigated owing to their controllable molecular design, tailored porous structures, good absorption of solar light, and low thermal conductivity. A variety of POP, such as conjugated microporous polymers (CMP), covalent organic frameworks (COF), hyper-crosslinked porous polymers (HCP), polymers of intrinsic microporosity (PIM), porous ionic polymers (PIP), are developed and applied in photothermal conversion applications of seawater desalination, latent energy storage, and biomedical fields. In this review, a comprehensive overview of the recent advances in POP for photothermal conversion is provided. The micro molecular structure characteristics and macro morphology of POP are designed for applications such as seawater desalination, latent heat energy storage, phototherapy and photodynamic therapy, and drug delivery. Besides, a probe into the underlying mechanism of structural design for constructing POP with excellent photothermal conversion performance is methodicalized. Finally, the remaining challenges and prospective opportunities for the future development of POP for solar energy-driven photothermal conversion applications are elucidated.

Advances in the Applications of Clinoptilolite-Rich Tuffs.

Adsorptive, catalytic, and antibacterial properties of clinoptilolite-rich tuffs (ZT) are presented here. ZT transformed into Fe-containing ZT (Fe-ZT) removes various organic and inorganic anions from water. Fe-ZT, which contains selenium, is beneficial for growing Pleurotus ostreatus mushrooms. The fungi convert inorganic Se from Fe-ZT into a more useful organically bonded form. ZT and Fe-ZT as supplements retain nitrogen and potassium in sandy, silty loam and silty clay soils. ZT shows an affinity toward toxic metal cations, which are essential for cleaning contaminated water. The adsorption of atenolol, acetylsalicylic, and salicylic acid onto M-ZT (M-Cu2+, Mn2+, Ni2+, or Zn2+) from water solutions suggests that both the natures of M and pharmaceuticals have a significant impact on the adsorption mechanism and determine the adsorption capability of the ZT. ZT is an excellent carrier for ultrafine (2-5 nm) nano oxide particles, which have been shown to have catalytic activity in different chemical processes and photodegradation reactions of organic pollutants. ZT can also be transformed into SO4-SnO2-ZT, which is catalytically active as a solid acid. M-ZT is an effective carrier of valuable bacteria. Ag-ZT possesses beneficial bactericidal activity in disinfecting water and soil remediation.

Green synthesis of iron nanoparticles using mulberry leaf extract: characterization, identification of active biomolecules, and catalytic activity.

The synthesis of iron-based nanoparticles (Fe NPs) using traditional preparation methods suffered from the disadvantages of high cost, environmental harm, and easy agglomeration. In this study, a novel eco-friendly method was proposed for the synthesis of iron nanomaterials (ML-Fe NPs): using antioxidant components extracted from mulberry leaf to reduce divalent iron (II). The preparation conditions of ML-Fe NPs were optimized by orthogonal tests. The prepared ML-Fe NPs exhibited an amorphous core-shell structure, displaying excellent dispersion and stability. During the synthesis process of ML-Fe NPs, the polyphenol molecules in mulberry leaf extract played a dominant role. A possible synthetic mechanism involving complexation, reduction, and encapsulation was proposed. Furthermore, the ML-Fe NPs were utilized to construct an ML-Fe NPs/peroxymonosulfate catalytic system for the degradation of Rhodamine B dye wastewater. The ML-Fe NPs demonstrated remarkable catalytic potential, achieving a 99% degradation efficiency for Rhodamine B within a span of 40 min.

Structuring vegetable oils through enzymatic glycerolysis for water-in-oil emulsions.

Enzymatic glycerolysis is a biotechnological process for structuring vegetable oils. This study investigates the kinetics of glycerolysis of peanut oil and explores the potential of the resulting structured oil to enhance the physical stability of water-in-oil emulsions. Using a 1:1 glycerol-to-oil molar ratio and 4 % lipase B from Candida antarctica as a catalyst, the reaction was conducted at 65 °C with stirring at 400 rpm. Acylglyceride fractions changes were quantified through NMR and DSC. Fat crystal formation was observed using scanning electron microscopy. The results revealed a first-order decay pattern, converting triglycerides into monoacylglycerides and diacylglycerides in less than 16 h. Subsequently, water-in-oil emulsions prepared with glycerolized oil showed augmented stability through multiple light scattering techniques and visual assessment. The structured oils effectively delayed phase separation, highlighting the potential of glycerolysis in developing vegetable oil-based emulsions with improved functional properties and reduced saturated fatty acid content.

Computational Study Into the Oxidative Ring-Closure Mechanism During the Biosynthesis of Deoxypodophyllotoxin.

The nonheme iron dioxygenase deoxypodophyllotoxin synthase performs an oxidative ring-closure reaction as part of natural product synthesis in plants. How the enzyme enables the oxidative ring-closure reaction of (-)-yatein and avoids substrate hydroxylation remains unknown. To gain insight into the reaction mechanism and understand the details of the pathways leading to products and by-products we performed a comprehensive computational study. The work shows that substrate is bound tightly into the substrate binding pocket with the C7'-H bond closest to the iron(IV)-oxo species. The reaction proceeds through a radical mechanism starting with hydrogen atom abstraction from the C7'-H position followed by ring-closure and a final hydrogen transfer to form iron(II)-water and deoxypodophyllotoxin. Alternative mechanisms including substrate hydroxylation and an electron transfer pathway were explored but found to be higher in energy. The mechanism is guided by electrostatic perturbations of charged residues in the second-coordination sphere that prevent alternative pathways.

Recent advances in ambient-stable black phosphorus materials for artificial catalytic nitrogen cycle in environment and energy.

Nitrogen cycle is crucial for the Earth's ecosystem and human-nature coexistence. However, excessive fertilizer use and industrial contamination disrupt this balance. Semiconductor-based artificial nitrogen cycle strategies are being actively researched to address this issue. Black phosphorus (BP) exhibits remarkable performance and significant potential in this area due to its unique physical and chemical properties. Nevertheless, its practical application is hindered by ambient instability. This review covers the synthesis methods of BP materials, analyzes their instability factors under environmental conditions, discusses stability improvement strategies, and provides an overview of the applications of ambient-stable BP materials in nitrogen cycle, including N2 fixation, NO3- reduction, NOx removal and nitrides sensing. The review concludes by summarizing the challenges and prospects of BP materials in the nitrogen cycle, offering valuable guidance to researchers.

A sustainable strategy for biosynthesis of Rebaudioside D using a novel glycosyltransferase of Solanum tuberosum.

Bioconversion of Rebaudioside D faces high-cost obstacles. Herein, a novel glycosyltransferase StUGT converting Rebaudioside A to Rebaudioside D was screened and characterized, which exhibits stronger affinity and substrate specificity for Rebaudioside A than previously reported enzymes. A whole-cell catalytic system was thus developed using the StUGT strain. The production of Rebaudioside D was enhanced significantly by enhancing cell permeability, and the maximum production of 6.12 g/L and the highest yield of 98.08% by cell catalyst was obtained by statistical-based optimization. A new cascade process utilizing this recombinant strain and E. coli expressing sucrose synthase was further established to reduce cost through replacing expensive UDPG with sucrose. A StUGT-GsSUS1 system exhibited high catalytic capability, and 5.27 g L-1 Rebaudioside D was achieved finally without UDPG addition by systematic optimization. This is the best performance reported in cell-cascaded biosynthesis, which paves a new cost-effective strategy for sustainable synthesis of scarce premium sweeteners from biomass.

Enhanced permanganate oxidation of phenolic pollutants by alumina and potential industrial application.

In this study, we found that alumina (Al2O3) may improve the degradation of phenolic pollutants by KMnO4 oxidation. In KMnO4/Al2O3 system, the removal efficiency of 2,4-Dibromophenol (2,4-DBP) was increased by 26.5%, and the apparent activation energy was decreased from 44.5 kJ/mol to 30.9 kJ/mol. The mechanism of Al2O3-catalytic was elucidated by electrochemical processes, X-ray photoelectron spectroscopy (XPS) characterization and theoretical analysis that the oxidation potential of MnO4- was improved from 0.46 V to 0.49 V. The improvement was attributed to the formation of coordination bonds between the O atoms in MnO4- and the empty P orbitals of the Al atoms in Al2O3 crystal leading to the even-more electron deficient state of MnO4-. The excellent reusability of Al2O3, the good performance on degradation of 2,4-DBP in real water, the satisfactory degradation of fixed-bed reactor, and the enhanced removal of 6 other phenolic pollutants demonstrated that the KMnO4/Al2O3 system has satisfactory potential industrial application value. This study offers evidence for the improvement of highly-efficient MnO4- oxidation systems.

Characterization of the active site in the thiocyanate-forming protein from Thlaspi arvense (TaTFP) using EPR spectroscopy.

Glucosinolates are plant thioglucosides, which act as chemical defenses. Upon tissue damage, their myrosinase-catalyzed hydrolysis yields aglucones that rearrange to toxic isothiocyanates. Specifier proteins such as thiocyanate-forming protein from Thlaspi arvense (TaTFP) are non-heme iron proteins, which capture the aglucone to form alternative products, e.g. nitriles or thiocyanates. To resolve the electronic state of the bound iron cofactor in TaTFP, we applied continuous wave electron paramagnetic resonance (CW EPR) spectroscopy at X-and Q-band frequencies (∼9.4 and ∼34 GHz). We found characteristic features of high spin and low spin states of a d 5 electronic configuration and local rhombic symmetry during catalysis. We monitored the oxidation states of bound iron during conversion of allylglucosinolate by myrosinase and TaTFP in presence and absence of supplemented Fe2+. Without added Fe2+, most high spin features of bound Fe3+ were preserved, while different g'-values of the low spin part indicated slight rearrangements in the coordination sphere and/or structural geometry. We also examined involvement of the redox pair Fe3+/Fe2 in samples with supplemented Fe2+. The absence of any EPR signal related to Fe3+ or Fe2+ using an iron-binding deficient TaTFP variant allowed us to conclude that recorded EPR signals originated from the bound iron cofactor.

Recent Advances in Asymmetric Catalysis Using p-Block Elements.

The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone of organic synthesis. Typically, metal catalysts bearing chiral ligands as well as chiral organocatalysts have been employed for the enantioselective synthesis of organic compounds. In this review, we highlight the recent advances in main group catalysis for enantioselective reactions using the p-block elements (boron, aluminium, phosphorus, bismuth) as a complementary and sustainable approach to generate chiral molecules. Several of these catalysts benefit in terms of high abundance, low toxicity, high selectivity, and excellent reactivity. This minireview summarises the utilisation of chiral p-block element catalysts for asymmetric reactions to generate value-added compounds.

Magnetic activated carbon from spent coffee grounds: iron-catalyzed CO2 activation mechanism and adsorption of antibiotic lomefloxacin from aqueous medium.

The facile fabrication of low-cost adsorbents possessing high removal efficiency and convenient separation property is an urgent need for water treatment. Herein, magnetic activated carbon was synthesized from spent coffee grounds (SCG) by Fe-catalyzed CO2 activation at 800 °C for 90 min, and magnetization and pore formation were simultaneously achieved during heat treatment. The sample was characterized by N2 adsorption-desorption, XRD, VSM, SEM, and FTIR. Batch adsorption experiments were conducted using lomefloxacin (LMO) as the probing pollutant. Preparation mechanism was revealed by TG-FTIR and XRD. Experimental results showed that Fe3O4 derived from Fe species can be reduced to Fe by carbon at high temperatures, followed by subsequent reoxidation to Fe3O4 by CO2, and the redox cycle between Fe and Fe3O4 favored the formation of pores. The promotion effects of Fe species on CO2 activation can be quantitatively reflected by the yield of CO as the signature gaseous product, and the suitable activation temperate range was determined to be 675 to 985 °C. The BET surface area, total pore volume, and saturated magnetization value of the product were 586 m2 g-1, 0.327 cm3 g-1, and 11.59 emu g-1, respectively. The Langmuir model was applicable for the adsorption isotherm data for LMO with the maximum adsorption capacity of 95 mg g-1, and thermodynamic analysis revealed that the adsorption process was endothermic and spontaneous. This study demonstrated that Fe-catalyzed CO2 activation was an effective method of converting SCG into magnetic separable adsorbent for LMO removal from aqueous medium.

Differential molecular mechanisms of substrate recognition by selenium methyltransferases, INMT and TPMT, in selenium detoxification and excretion.

It is known that the recommended dietary allowance of selenium (Se) is dangerously close to its tolerable upper intake level. Se is detoxified and excreted in urine as trimethylselenonium ion (TMSe) when the amount ingested exceeds the nutritional level. Recently, we demonstrated that the production of TMSe requires two methyltransferases: thiopurine S-methyltransferase (TPMT) and indolethylamine N-methyltransferase (INMT). In this study, we investigated the substrate recognition mechanisms of INMT and TPMT in the Se-methylation reaction. Examination of the Se-methyltransferase activities of two paralogs of INMT, namely, nicotinamide N-methyltransferase and phenylethanolamine N-methyltransferase, revealed that only INMT exhibited Se-methyltransferase activity. Consistently, molecular dynamics simulations demonstrated that dimethylselenide was preferentially associated with the active center of INMT. Using the fragment molecular orbital method, we identified hydrophobic residues involved in the binding of dimethylselenide to the active center of INMT. The INMT-L164R mutation resulted in a deficiency in Se- and N-methyltransferase activities. Similarly, TPMT-R152, which occupies the same position as INMT-L164, played a crucial role in the Se-methyltransferase activity of TPMT. Our findings suggest that TPMT recognizes negatively charged substrates, whereas INMT recognizes electrically neutral substrates in the hydrophobic active center embedded within the protein. These observations explain the sequential requirement of the two methyltransferases in producing TMSe.

Phosphorus Chemistry at the Roots of Bioenergetics: Ligand Permutation as the Molecular Basis of the Mechanism of ATP Synthesis/Hydrolysis by FOF1-ATP Synthase.

The integration of phosphorus chemistry with the mechanism of ATP synthesis/hydrolysis requires dynamical information during ATP turnover and catalysis. Oxygen exchange reactions occurring at ß-catalytic sites of the FOF1-ATP synthase/F1-ATPase imprint a unique record of molecular events during the catalytic cycle of ATP synthesis/hydrolysis. They have been shown to provide valuable time-resolved information on enzyme catalysis during ATP synthesis and ATP hydrolysis. The present work conducts new experiments on oxygen exchange catalyzed by submitochondrial particles designed to (i) measure the relative rates of Pi-ATP, Pi-HOH, and ATP-HOH isotope exchanges; (ii) probe the effect of ADP removal on the extent of inhibition of the exchanges, and (iii) test their uncoupler sensitivity/resistance. The objectives have been realized based on new experiments on submitochondrial particles, which show that both the Pi-HOH and ATP-HOH exchanges occur at a considerably higher rate relative to the Pi-ATP exchange, an observation that cannot be explained by previous mechanisms. A unifying explanation of the kinetic data that rationalizes these observations is given. The experimental results in (ii) show that ADP removal does not inhibit the intermediate Pi-HOH exchange when ATP and submitochondrial particles are incubated, and that the nucleotide requirement of the intermediate Pi-HOH exchange is adequately met by ATP, but not by ADP. These results contradicts the central postulate in Boyer's binding change mechanism of reversible catalysis at a F1 catalytic site with Keq~1 that predicts an absolute requirement of ADP for the occurrence of the Pi-HOH exchange. The prominent intermediate Pi-HOH exchange occurring under hydrolytic conditions is shown to be best explained by Nath's torsional mechanism of energy transduction and ATP synthesis/hydrolysis, which postulates an essentially irreversible cleavage of ATP by mitochondria/particles, independent from a reversible formation of ATP from ADP and Pi. The explanation within the torsional mechanism is also shown to rationalize the relative insensitivity of the intermediate Pi-HOH exchange to uncouplers observed in the experiments in (iii) compared to the Pi-ATP and ATP-HOH exchanges. This is shown to lead to new concepts and perspectives based on ligand displacement/substitution and ligand permutation for the elucidation of the oxygen exchange reactions within the framework of fundamental phosphorus chemistry. Fast mechanisms that realize the rotation/twist, tilt, permutation and switch of ligands, as well as inversion at the γ-phosphorus synchronously and simultaneously and in a concerted manner, have been proposed, and their stereochemical consequences have been analyzed. These considerations take us beyond the binding change mechanism of ATP synthesis/hydrolysis in bioenergetics.

Green Synthesis of CuO Nanoparticles Using Agaricus bisporus Extract as a Highly Efficient Catalyst for the Suzuki Cross-Coupling Reaction.

Copper oxide nanoparticles (CuONPs) were synthesized using a rapid, eco-friendly, cost-effective, efficient, and biological method employing aqueous Agaricus bisporus extract as a capping and reducing agent. The formation of CuONPs was checked by UV-vis spectroscopy and was characterized by X-ray diffraction analysis (XRD), dynamic light scattering spectroscopy (DLS), transmission electron microscopy (TEM), and surface area and porosimetry analyzer. The characterization results showed that the synthesized nanoparticles had a spherical-like appearance and a crystal structure with 40-100 nm particle size. The green synthesized CuONPs were found to be an excellent and sustainable heterogeneous catalyst (TOF up to 29700 h-1 ) for the Suzuki C-C coupling of aryl halides with phenylboronic acid in a very short reaction time (10 minutes). Moreover, the easily recovered catalyst can be reused five times with just a negligible reduction in catalytic behavior.

A review of physical, chemical and biological synthesis methods of bimetallic nanoparticles and applications in sensing, water treatment, biomedicine, catalysis and hydrogen storage.

This article provides an in-depth analysis of various fabrication methods of bimetallic nanoparticles (BNP), including chemical, biological, and physical techniques. The review explores BNP's diverse uses, from well-known applications such as sensing water treatment and biomedical uses to less-studied areas like breath sensing for diabetes monitoring and hydrogen storage. It cites results from over 1000 researchers worldwide and >300 peer-reviewed articles. Additionally, the article discusses current trends, actionable recommendations, and the importance of synthetic analysis for industry players looking to optimize manufacturing techniques for specific applications. The article also evaluates the pros and cons of various fabrication methods, highlighting the potential of plant extract synthesis for mass production of capped BNPs. However, it warns that this method may not be suitable for certain applications requiring ligand-free surfaces. In contrast, physical methods like laser ablation offer better control and reactivity, especially for applications where ligand-free surfaces are critical. The report underscores the environmental benefits of plant extract synthesis compared to chemical methods that use hazardous chemicals and pose risks to extraction, production, and disposal. The article emphasizes the need for life cycle assessment (LCA) articles in the literature, given the growing volume of research on nanotechnology materials. This article caters to researchers at all stages and applies to various fields applying nanomaterials.

Using the Colloidal Method to Prepare Au Catalysts for the Alkylation of Aniline by Benzyl Alcohol.

Using the colloidal method, attempts were made to deposit Au NPs on seven different material supports (TiO2, α and γ-Al2O3, HFeO2, CeO2, C, and SiO2). The deposition between 0.8 and 1 wt% of Au NPs can be generally achieved, apart for SiO2 (no deposition) and α-alumina (0.3 wt%). The resultant sizes of the Au NPs were dependent on the nature as well as the surface area of the support. The catalytic activity and selectivity of the supported Au catalysts were then compared in the alkylation of aniline by benzyl alcohol. Correlations were made between the nature of the support, the size of the Au NP, and the H-binding energy. A minimum H-binding energy of 1100 µV K-1 was found to be necessary for high selectivity for the secondary amine. Comparisons of the TEM images of the pre- and post-reaction catalysts also revealed the extent of Au NP agglomeration under the reaction conditions.

Probing conformational kinetics of catalase with and without magnetic field by single-entity collision electrochemistry.

The conformational motions of enzymes are crucial for their catalytic activities, but these fluctuations are usually spontaneous and unsynchronized and thus difficult to obtain from ensemble-averaged measurements. Here, we employ label-free single-entity electrochemical measurements to monitor in real time the fluctuating enzymatic behavior of single catalase molecules toward the degradation of hydrogen peroxide. By probing the electrochemical signals of single catalase molecules at a carbon nanoelectrode, we were able to observe three distinct current traces that could be attributed to conformational changes on the sub-millisecond timescale. Whereas, nearly uniform single long peaks were observed for single catalase molecules under a moderate magnetic field due to the restricted conformational changes of catalase. By combining high-resolution current signals with a multiphysics simulation model, we studied the catalytic kinetics of catalase with and without a magnetic field, and further estimated the maximum catalytic rate and conformational transition rate. This work introduces a new complementary approach to existing single-molecule enzymology, giving further insight into the enzymatic reaction mechanism.

Cobalt-aluminum spinel supported on modified γ-alumina for peroxymonosulfate activation: Si-Al ratio of support to optimize performance and reusability.

The development of cobalt-based supported catalysts with high PMS catalytic activity and stability by adjusting the composition of the support is highly desirable yet remains scarce. In the work, a series of catalysts (Co2AlO4/Al2O3-xSiO2) were prepared by impregnation and high-temperature calcination using Al2O3-xSiO2 with a low Si-Al ratio as the support. Measurement techniques such as XRD, XPS, UV-DRS, FTIR, BET, SEM and HRTEM were used to characterize textural and chemical properties (ratio of Co3+/Co2+, specific surface area, pore size, pore volume, etc.). The ratio of Co3+/Co2+ and pore volume of Co2AlO4/Al2O3-xSiO2 can be turned by controlling the ratio of Si to Al, which are closely related to the catalytic performance and reusability of the catalysts. The optimized catalyst (Co2AlO4/Al2O3-0.25SiO2) can completely degrade 10 mg/L p-nitrophenol (PNP) in 40 min in the pH range of 3-9 with excellent reusability. The effects of several reaction parameters (i.e., PMS dosage, Co2AlO4/Al2O3-0.25SiO2 dosage, reaction temperature, initial pH value, and inorganic ions) on PNP removal were comprehensively investigated. Sulfate radical (SO4•-) and singlet oxygen (1O2) are making a major contribution to the degradation of PNP. Moreover, a millimeter-scale catalyst (CoSiAl-0.25/Al2O3 pellet) was prepared by sol adsorption and high-temperature calcination method, which maintained high oxidation activity after treatment of 18 L wastewater (PNP of 10 mg/L) in a continuous flow process. The method is simple and easy to operate on a large scale, providing a new perspective on the design and preparation of cobalt-aluminum spinel catalysts for activated PMS.

Phosphorus doped cyanobacterial biochar catalyzes efficient persulfate oxidation of the antibiotic norfloxacin.

In this study, cyanobacterial biochars (CBs) enriched/doped with non-metallic elements were prepared by pyrolysis of biomass amended with different N, S, and P containing compounds. Their catalytic reactivity was tested for persulfate oxidation of the antibiotic norfloxacin (NOR). N and S doping failed to improve CB catalytic reactivity, while P doping increased reactivity 5 times compared with un-doped biochar. Biochars produced with organic phosphorus dopants showed the highest reactivity. Post-acid-washing improved catalytic reactivity. In particular, 950 ℃ acid-washed triphenyl-phosphate doped CB showed the largest degradation rate and reached 79% NOR mineralization in 2 h. Main attributes for P-doped CBs high reactivity were large specific surface areas (up to 655 m2/g), high adsorption, high C-P-O content, graphitic P and non-radical degradation pathway (electron transfer). This study demonstrates a new way to reuse waste biomass by producing efficient P-doped metal-free biochars and presents a basic framework for designing carbon-based catalysts for organic pollutant degradation.