Catalyst design and structure control for photocatalytic refineries of cellulosic biomass to fuels and chemicals

Lignocellulosic biomass is the largest renewable hydrocarbon resource on earth.Converting cellulose,one of the major components of lignocellulose,powered by solar energy is a promising way of providing lowcarbon-footprint energy chemicals such as H_(2),HCOOH,CO,and transportation fuels.State-of-the-art biorefineries target the full use of biomass feedstocks as they have a maximum collection radius of 75-100 km,requesting efficient and selective photocatalysts that significantly influence the outcome of photocatalytic biorefineries.Well-performed photocatalysts can harvest a broad solar spectrum and are active in breaking the chemical bonds of cellulose,decreasing the capital investments of biorefineries.Besides,photocatalysts should control the selectivity of cellulose conversion,originating target products to level down separation costs.Charge separation in photocatalysts and interfacial charge transfer between photocatalysts and cellulose affect the activity and selectivity of cellulose refineries to H2 and carbonaceous chemicals.To account for the challenges above,this review summarizes photocatalysts for the refineries of cellulose and downstream platform molecules based on the types of products,with the structure features of different types of photocatalysts discussed in relation to the targets of either improving the activity or product selectivity.In addition,this review also sheds light on the methods for designing and regulating photocatalyst structures to facilitate photocatalytic refineries of cellulose and platform molecules,meanwhile summarizing proposed future research challenges and opportunities for designing efficient photocatalysts.

Preparation and properties of high-energy-density aluminum/boroncontaining gelled fuels

Energetic nanofluid fuel has caught the attention of the field of aerospace liquid propellant for its high energy density(HED), but it suffers from the inevitable solid-liquid phase separation problem. To resolve this problem, herein we synthesized the high-Al-/B-containing(up to 30%(mass)) HED gelled fuels, with low-molecular-mass organic gellant Z, which show high net heat of combustion(NHOC), density, storage stability, and thixotropic properties. The characterizations indicate that the application of energetic particles to the gelled fuels obviously destroys their fibrous network structures but can provide the new particle-gellant gelation microstructures, resulting in the comparable stability between 1.0%(mass) Z/JP-10 + 30%(mass) Al or B and pure JP-10 gelled fuel. Moreover, the gelled fuels with high-content Al or B exhibit high shear-thinning property, recovery capability, and mechanical strength, which are favorable for their storage and utilization. Importantly, the prepared 1.0%(mass) Z/JP-10 + 30%(mass) B(or 1.0%(mass) Z/JP-10 + 30%(mass) Al) shows the density and NHOC 1.27 times(1.30) and 1.43 times(1.21)higher than pure JP-10, respectively. This work provides a facile and valid approach to the manufacturing of HED gelled fuels with high content of energetic particles for gel propellants.

CO_(2) conversion to solar fuels and chemicals:Opening the new paths

This future article discusses the new prospects and directions of CO_(2)conversion via the photo-electrocatalytic(PEC)route.The second(2nd)generation solar fuels and chemicals(SFs)are generated directly in PEC systems via electrons/protons reactions without forming molecular H_(2)as an intermediate,overcoming the thermodynamics limitations and practical issues encountered for electro-fuels produced by multistep thermocatalytic processes(i.e.CO_(2)conversion with H_(2)coming from water electrolysis).A distributed and decentralized production of SFs requires very compact,highly integrated,and intensified technologies.Among the existing reactors of advanced design(based on artificial leaves or photosynthesis),the integrated photovoltaic plus electrocatalytic(PV-EC)device is the only system(demonstrated at large scale)to produce SFs with high solar-to-fuel(STF)efficiency.However,while the literature indicates STF efficiency as the main(and only)measure of process performance,we remark here the need to refer to productivity(in terms of current density)and make tests with reliable flow PEC systems(with electrodes of at least 5–10 cm^(2))to accelerate the scaling-up process.Using approaches that minimize downstream separation costs is also mandatory.Many limitations exist in PEC systems,but most can be overcome by proper electrode and cell engineering,thus going beyond the properties of the electrocatalysts.As examples of current developments,we present the progress of(i)artificial leaf/tree devices for green H_(2)distributed production and(ii)a PEC device producing the same chemicals at both cathode and anode parts without downstream operations for green solvent distributed production.Based on these developments,future directions,such as producing fertilizers and food components from the air,are outlined.The aim is to provide new ideas and research directions from a personal perspective.

Past, Present and Future: A Role for Liquid Biofuels in Transitioning to Net Zero?

Over the last decade, the uptake rate of first-generation biofuels (ethanol and biodiesel) has decelerated as low blend limits have increased only slowly and extreme volatility in oil prices has limited investment in biofuels production infrastructure. Concerns over the environmental impacts of large-scale biofuels production combined with tariff barriers have greatly restricted the global trade in biofuels. First-generation biofuels produced either by fermentation of sugars from maize or sugarcane (ethanol) or transesterification of triglycerides (biodiesel) presently contribute less than 4% of terrestrial transportation fuel demand and techno-economic modelling foresees this only slowly increasing by 2035. With internal combustion and diesel engines widely anticipated as being phased out in favour of electric power for motor vehicles, a much-reduced market demand for biofuels is likely if global demand for all liquid fuels declines by 2050. However, second-generation, thermochemically produced and biomass-derived fuels (renewable diesel, marine oils and sustainable aviation fuel) have much higher blend limits;combined with policies to decarbonise the aviation and marine industries, major new markets for these products in terrestrial, marine and aviation sectors may emerge in the second half of the 21st century.

Tandem hydroalkylation and deoxygenation of lignin-derived phenolics to synthesize high-density fuels

Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels using simulated lignin cracked oil in tandem with hydroalkylation and deoxygenation reactions.First,we investigated the reaction pathway for the hydroalkylation of phenol,which competes with the hydrodeoxygenation form cyclohexane.And then,we investigated the effects of metal catalyst types,the loading amount of metallic,acid dosage,and reactant ratio on the reaction results.The phenol hydroalkylation and hydrodeoxygenation were balanced when 180℃ and 5 MPa H_(2)with the alkanes yield of 95%.By extending the substrate to other lignin-derived phenolics and simulated lignin cracked oil,we obtained the polycyclic alkane fuel with high density of 0.918 g·ml^(-1)and calorific value of41.2 MJ·L^(-1).Besides,the fuel has good low-temperature properties(viscosity of 9.3 mm^(2)·s^(-1)at 20℃ and freezing point below-55℃),which is expected to be used as jet fuel.This work provides a promising way for the easy and green production of high-density fuel directly from real lignin oil.

Effects of nano-metal oxide additives on ignition and combustion properties of MICs-boron rich fuels

Boron has been considered a promising powdered metal fuel for enhancing composite propellants'energy output due to its high energy density.However,the high ignition temperature and low combustion efficiency limit the application of boron powder due to the high boiling point of the boron oxide layer.Much research is ongoing to overcome these shortcomings,and one potential approach is to introduce a small quantity of metal oxide additives to promote the reaction of boron.This study prepared boron-rich fuels with 10 wt%of eight nano-metal oxide additives by mechanical ball milling.The effect of metal oxides on the thermo-oxidation,ignition,and combustion properties of boron powder was comprehensively studied by the thermogravimetric analysis(TG),the electrically heated filament setup(T-jump),and the laser-induced combustion experiments.TG experiments at 5 K/min found that Bi_(2)O_(3),MoO_(3),TiO_(2),Fe_(2)O_(3),and CuO can promote thermo-oxidation of boron.Compared to pure boron,Tonsetcan be reduced from 569℃to a minimum of 449℃(B/Bi_(2)O_(3)).Infrared temperature measurement in T-jump tests showed that when heated by an electric heating wire at rates from 1000 K/s to 25000 K/s,the ignition temperatures of B/Bi_(2)O_(3) are the lowest,even lower than the melting point of boron oxide.Ignition images and SEM for the products further showed that the high heating rate is beneficial to the rapid reaction of boron powder in the single-particle combustion state.Fuels(B/Bi_(2)O_(3),B/MoO_(3),and B/CuO)were mixed with the oxidant AP and ignited by laser to study the combustion performance.The results showed that B/CuO/AP has the largest flame area,the highest BO_(2) characteristic spectral intensity,and the largest burn rate for powder lines.To combine the advantages of CuO and Bi_(2)O_(3),binary metal oxide(CBO,mass ratio of 3:1)was prepared and the test results showed that CBO can very well improve both ignition and combustion properties of boron.Especially B/CBO/AP has the highest burn rate compared with all fuels containing other additives.It was found that multi-component metal-oxide additive can more synergistically improve the reaction characteristics of boron powder than unary additive.These findings contribute to the development of boron-rich fuels and their application in propellants.

Explosion characteristics of aluminum-based activated fuels containing fluorine

Measuring the dust explosion characteristics of aluminum-based activated fuels was a prerequisite for developing effective prevention and control measures.In this paper,ignition sensitivity,flame propagation behaviors and explosion severity of aluminum/polytetrafluoroethylene(Al/PTFE)compositions including 2 PT(2.80 wt.%F),4 PT(7.18 wt.%F)and 8 PT(11.90 wt.%F)were studied.When the content of F increased from 2.80 wt.%to 11.90 wt.%,the minimum explosive concentration MEC decreased from380 g/m^(3)to 140 g/m^(3),due to the dual effects of increased internal active aluminum and enhanced reactivity.The average flame propagation velocities increased as the percentage of F increased.The maximum explosion pressure Pmof 500 g/m3aluminum-based activated fuels increased from 247 k Pa to299 kPa.Scanning electron microscopy demonstrated that with the increase of PTFE content,the reaction was more complete.On this basis,the explosion mechanism of aluminum-based activated fuels was revealed.

Synthesis of high density and low freezing point jet fuels range cycloalkanes with cyclopentanone and lignin-derived vanillins

In this work,a“cyclopentanone-vanillin”strategy was proposed for the preparation of jet fuel range cycloalkanes from lignocellulose-derived ketones and lignin-derived aldehydes via aldol condensation and hydrodeoxygenation(HDO).Ethanolamine lactate ionic liquid(LAIL)exhibited excellent catalytic activity in the aldol condensation of cyclopentanone and vanillin.Desired mono-condensation and bicondensation products were obtained with yield of 95.2%at 100℃.It is found that the synergy effects between amino group of ethanolamine and hydroxyl group of lactic acid play a key role in the aldol condensation.The condensation products were converted into cycloalkanes by HDO over 5%Pd/Nb_(2)O_(5)catalyst.The density of the obtained HDO products is 0.89 g/cm^(3)and the freezing point is lower than-60℃.These results suggest that the resulted cycloalkanes can be used as additives to improve the density and low-temperature fluidity of the jet fuels.

Harnessing dimethyl ether and methyl formate fuels for direct electrochemical energy conversion

In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-metallic alloy catalyst,Pt_(3)Pd_(3)Sn_(2)/C,discovered earlier by us.The current obtained during the bulk oxidation of a DME-saturated 1 M MF was higher than the summation of the currents provided by the two fuels separately,suggesting the cooperative effect of mixing these fuels.A significant increase in the anodic charge was realized during oxidative stripping of a pre-adsorbed DME+MF mixture as compared to DME or MF individually.This is ascribed to greater utilization of specific catalytic sites on account of the relatively lower adsorption energy of the dual-molecules than of the sum of the individual molecules as confirmed by the density fu nctional theory(DFT) calculations.Fuel cell polarization was also conducted using a Pt_(3)Pd_(3)Sn_(2)/C(anode) and Pt/C(cathode) catalysts-coated membrane(CCM).The enhanced surface coverage and active site utilization resulted in providing a higher peak power density by the DME+MF mixture-fed fuel cell(123 mW cm^(-2)at 0.45 V) than with DME(84mW cm^(-2)at 0.35 V) or MF(28 mW cm^(-2)at 0.2 V) at the same total anode hydrocarbon flow rate,temperature,and ambient pressure.

A Preliminary Study on Intensive Curing with Alcohol-based Fuels

The research investigated application effects of alcohol-based fuels in in- tensive curing. The results showed that alcohol-based fuels allow flexible adjustment of temperature and heat supplying. What＇s more, in treatment A, the cured tobac- cos are softer and brighter, with more oil content and higher proportion of first-class tobaccos. Per leaf weight increased by 0.13 g and output value per kang （a heat- able brick bed） deducting energy cost grew by 188.66 yuan. In addition, the con- tents of reducing sugar and potassium enhanced within the ranges of high-quality tobacco, and chemical components are more coordinated.

Transforming catalysis to produce e‐fuels:Prospects and gaps

After short introducing the crucial role of e‐fuels to meet net‐zero emissions targets,this perspective paper discusses the differences between reactive catalysis(electro‐,photo‐and plasma‐catalysis,with focus on the first for conciseness)and thermal catalysis used at most.The main point is to evidence that to progress in producing e‐fuels,the gap is not in terms of scaling‐up and pilot testing,but rather in the fundamental needs to turn the current approach and methodologies to develop reactive catalysis,including from a mechanistic perspective,to go beyond the current methods largely derived from thermal catalysis.Developing thus new fundamental bases to understand reactive catalysis is the challenge to accelerate the progress in this area to enable the potential role towards a sustainable net‐zero emissions future.Some novel aspects are highlighted,but the general aim is rather to stimulate discussion in rethinking catalysis from an alternative perspective.

Modeling surface fuels moisture content in Pinus brutia stands

Fuel moisture content is an important variable for forest fires because it affects fuel ignition and fire behavior. In order to accurately predict fuel ignition potential, fuel moisture content must be assessed by evaluating fire spread, fireline intensity and fuel consumption.Our objective here is to model moisture content of surface fuels in normally stocked Calabrian pine(Pinus brutia Ten.) stands in relation to weather conditions, namely temperature, relative humidity, and wind speed in the Mugla province of Turkey. All surface fuels were categorized according to diameter classes and fuel types. Six fuel categories were defined: these were 0–0.3, 0.3–0.6, and0.6–1 cm diameter classes, and cone, surface litter, and duff. Plastic containers 15 9 20 cm in size with 1 9 1 mm mesh size were used. Samples were taken from 09:00 to19:00 h and weighed every 2 h with 0.01 g precision for10 days in August. At the end of the study, samples were taken to the laboratory, oven-dried at 105 °C for 24 h and weighed to obtain fuel-moisture contents. Weather measurements were taken from a fully automated weather station set up at the study site prior to the study. Correlation and regression analyses were carried out and models were developed to predict fuel moisture contents for desorption and adsorption phase for each fuel type categories. Practical fuel moisture prediction models were developed for dry period. Models were developed that performed well with reasonable accuracy, explaining up to 92 and 95.6%of the variability in fuel-moisture contents for desorption and adsorption phases, respectively. Validation of the models were conducted using an independent data set and known fuel moisture prediction models. The predictive power of the models was satisfactory with mean absolute error values being 1.48 and 1.02 for desorption and adsorption as compared to the 2.05 and 1.60 values for the Van Wagner's hourly litter moisture content prediction model. Results obtained in this study will be invaluable for fire management planning and modeling.

Recent advances on the reduction of CO2 to important C2+ oxygenated chemicals and fuels

The chemical utilization of CO_2 is a crucial step for the recycling of carbon resource. In recent years, the study on the conversion of CO_2 into a wide variety of C_(2+) important chemicals and fuels has received considerable attention as an emerging technology. Since CO_2 is thermodynamically stable and kinetically inert, the effective activation of CO_2 molecule for the selective transformation to target products still remains a challenge. The welldesigned CO_2 reduction route and efficient catalyst system has imposed the feasibility of CO_2 conversion into C_(2+) chemicals and fuels. In this paper, we have reviewed the recent advances on chemical conversion of CO_2 into C_(2+) chemicals and fuels with wide practical applications, including important alcohols, acetic acid, dimethyl ether, olefins and gasoline. In particular, the synthetic routes for C\\C coupling and carbon chain growth, multifunctional catalyst design and reaction mechanisms are exclusively emphasized.

Electrocatalytic conversion of CO_2 to liquid fuels using nanocarbon-based electrodes

Recent advances on the use of nanocarbon-based electrodes for the electrocatalytic conversion of gaseous streams of CO2 to liquid fuels are discussed in this perspective paper. A novel gas-phase electrocatalytic cell, different from the typical electrochemical systems working in liquid phase, was developed. There are several advantages to work in gas phase, e.g. no need to recover the products from a liquid phase and no problems of CO2 solubility, etc. Operating under these conditions and using electrodes based on metal nanoparticles supported over carbon nanotube （CNT） type materials, long C-chain products （in particular isopropanol under optimized conditions, but also hydrocarbons up to C8-C9） were obtained from the reduction of CO2. Pt-CNT are more stable and give in some cases a higher productivity, but Fe-CNT, particular using N-doped carbon nanotubes, give excellent properties and are preferable to noble-metal-based electrocatalysts for the lower cost. The control of the localization of metal particles at the inner or outer surface of CNT is an importact factor for the product distribution. The nature of the nanocarbon substrate also plays a relevant role in enhancing the productivity and tuning the selectivity towards long C-chain products. The electrodes for the electrocatalytic conversion of CO2 are part of a photoelectrocatalytic （PEC） solar cell concept, aimed to develop knowledge for the new generation artificial leaf-type solar cells which can use sunlight and water to convert CO2 to fuels and chemicals. The CO2 reduction to liquid fuels by solar energy is a good attempt to introduce renewables into the existing energy and chemical infrastructures, having a higher energy density and easier transport/storage than other competing solutions （i.e. H2）.

Removal of CO from reformed fuels by selective methanation over Ni-B-Zr-O_δ catalysts

The Ni-B-Oδ and Ni-B-Zr-Oδ catalysts were prepared by the method of chemical reduction, and the deep removal of CO by selective methanation from the reformed fuels was performed over the as-prepared catalysts. The results showed that zirconium strongly influenced the activity and selectivity of the Ni-B-Zr-Oδ catalysts. Over the Ni-B-Oδ catalyst, the highest CO conversion obtained was only 24.32% under the experi-mental conditions studied. However, over the Ni-B-Zr-Oδ catalysts, the CO methanation conversion was higher than 90% when the temperature was increased to 220℃. Additionally, it was found that the Ni/B mole ratio also affected the performance of the Ni-B-Zr-Oδ catalysts. With the increase of the Ni/B mole ratio from 1.8 to 2.2, the CO methanation activity of the catalyst was improved. But when the Ni/B mole ratio was higher than 2.2, the performance of the catalyst for CO selective methanation decreased instead. Among all the catalysts, the Ni29B13Zr58Oδ catalyst investigated here exhibited the highest catalytic performance for the CO selective methanation, which was capable of reducing the CO outlet concentration to less than 40 ppm from the feed gases stream in the temperature range of 230-250℃, while the CO2 conversion was kept below 8% all along. Characterization of the Ni-B-Oδ and Ni-B-Zr-Oδ catalysts was provided by XRD, SEM, DSC, and XPS.

A review of physical supply and EROI of fossil fuels in China

This paper reviews China’s future fossil fuel supply from the perspectives of physical output and net energy output. Comprehensive analyses of physical output of fossil fuels suggest that China’s total oil production will likely reach its peak, at about 230 Mt/year(or 9.6 EJ/year),in 2018; its total gas production will peak at around350 Bcm/year(or 13.6 EJ/year) in 2040, while coal production will peak at about 4400 Mt/year(or 91.9 EJ/year)around 2020 or so. In terms of the forecast production of these fuels, there are significant differences among current studies. These differences can be mainly explained by different ultimately recoverable resources assumptions, the nature of the models used, and differences in the historical production data. Due to the future constraints on fossil fuels production, a large gap is projected to grow between domestic supply and demand, which will need to be met by increasing imports. Net energy analyses show that both coal and oil and gas production show a steady declining trend of EROI(energy return on investment) due to the depletion of shallow-buried coal resources and conventional oil and gas resources, which is generally consistent with the approaching peaks of physical production of fossil fuels. The peaks of fossil fuels production, coupled with the decline in EROI ratios, are likely to challenge the sustainable development of Chinese society unless new abundant energy resources with high EROI values can be found.

Recent advances in Cu-based nanocomposite photocatalysts for CO_2 conversion to solar fuels

COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COto useful solar fuels such as CO, CH, CHOH, and CHOH. Among studied formulations, Cubased photocatalysts are the most attractive for COconversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for COconversion, which includes metallic copper, copper alloy nanoparticles（NPs）, copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for COconversion with much-enhanced energy conversion efficiency and production rates.

Few‐layer carbon nitride photocatalysts for solar fuels and chemicals:Current status and prospects

Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites,few‐layer carbon nitride(FLCN)materials present great potential for production of solar fuels and chemicals and set off a new wave of research in the last few years.Herein,the recent progress in synthesis and regulation of FLCN‐based photocatalysts,and their applications in the conversion of sunlight into fuels and chemicals,is summarized.More importantly,the regulation strategies from chemical modification to microstructure control toward the production of solar fuels and chemicals has been deeply analyzed,aiming to inspire critical thinking about the effective approaches for photocatalyst modification rather than developing new materials.At the end,the key scientific challenges and some future trend of FLCN‐based materials as advanced photocatalysts are also discussed.

Heterogeneous Catalysis for CO_(2) Conversion into Chemicals and Fuels

Catalytic conversion of CO_(2)into chemicals and fuels is a viable method to reduce carbon emissions and achieve carbon neutrality.Through thermal catalysis,electrocatalysis,and photo(electro)catalysis,CO_(2)can be converted into a wide range of valuable products,including CO,formic acid,methanol,methane,ethanol,acetic acid,propanol,light olefi ns,aromatics,and gasoline,as well as fi ne chemicals.In this mini-review,we summarize the recent progress in heterogeneous catalysis for CO_(2)conversion into chemicals and fuels and highlight some representative studies of diff erent conversion routes.The structure-performance correlations of typical catalytic materials used for the CO_(2)conversion reactions have been revealed by combining advanced in situ/operando spectroscopy and microscopy characterizations and density functional theory cal-culations.Catalytic selectivity toward a single CO_(2)reduction product/fraction should be further improved at an industrially relevant CO_(2)conversion rate with considerable stability in the future.

Regulating the nanoscale intimacy of metal and acidic sites in Ru/γ-Al_(2)O_(3)for the selective conversions of lignin-derived phenols to jet fuels

Catalytic hydrodeoxygenation(HDO)of biomass-derived oxy-compounds to advanced hydrocarbon fuels usually requires bifunctional catalysts containing metals and acidic sites.The appropriate tuning of metal and/or acidic active sites at interfaces of bifunctional catalysts can significantly improve catalyst activity and product selectivity.Here,4-trifuoromethyl salicylic acid(TFMSA),as a hydrothermal stable organic acid,was employed to tailor the bifunctional interface of Ru/γ-Al_(2)O_(3)to enhance the catalytic performance on converting lignin-derived phenols to jet fuel range cycloalkanes.More than 80%phenol was converted into cyclohexane at 230°C for 1 h over Ru/γ-Al_(2)O_(3)modified by TFMSA,which was about three times higher than that over unmodified Ru/γ-Al_(2)O_(3).X-ray diffraction(XRD),Transmission electron microscope(TEM),H2 chemisorption,and energy dispersive X-ray spectroscopy(EDS)elemental mapping results indicated that Ru nanoparticles and TFMSA were well distributed onγ-Al_(2)O_(3),and a nanoscale intimacy between Ru and TFMSA was reached.Meanwhile,Fourier transform infrared spectroscopy after pyridine adsorption(Py-FT-IR)analysis proved that Brønsted acidic sites on the catalytic interfaces of TFMSA modified Ru/γ-Al_(2)O_(3)had been improved.Moreover,the kinetic and density functional theory(DFT)results suggested that the synergistic effects of adjacent Ru nanoparticles and acidic sites were crutial for promoting the rate-limiting conversion step of phenol HDO to cyclohexane.