Elsevier

Molecular Catalysis

Volume 483, March 2020, 110716
Molecular Catalysis

Review
Sustainable production of formic acid from biomass and carbon dioxide

https://doi.org/10.1016/j.mcat.2019.110716Get rights and content

Highlights

Abstract

Formic acid (FA) is a versatile molecule with widespread applications in both chemical industries and renewable energy fields. However, the commercial manufacture of FA is still based on non-renewable fossil feedstock, and thus alternative methods to obtain FA from renewable resources are highly desirable and attract significant scientific attentions. Biomass represents the largest carbon resource on Earth, and various strategies including acid hydrolysis, wet oxidation and catalytic oxidation have been developing to transform biomass resources into FA with relatively high yield and selectivity. Meanwhile, carbon dioxide (CO2) as an inexpensive and widely available C1 platform compound, is also a potential resource to produce FA via hydrogenation by different strategies such as chemical, photochemical and electrochemical catalysis. In this review, FA production from biomass resources especially cellulosic biomass will be systematically summarized according to the transformation methods. Following this, recent progresses in the CO2 valorization to generate FA will be generally illustrated. Finally, the catalytic dehydrogenation of FA to generate hydrogen as a clean and renewable energy fuel will be concisely mentioned since it exemplifies the critical role of FA in future energy restructure tactics.

Introduction

Among the 100 most important chemical compounds, formic acid (FA) is the simplest yet strongest organic acid with prominent advantages. It is more eco-friendly, noncorrosive, easily biodegradable, etc. than other organic and inorganic acids, and is broadly applied in agricultures, rubbery, pharmaceuticals, animal feeds, leather and textiles industries [1]. Moreover, it is a frequently-used reductant, green solvent as well as a building block in various chemical syntheses. In 2019, the approximate annual global market for FA is about US$ 620 million which would maintain a constant increase in the future. Not only being an important chemical commodity, FA is also a key energy carrier/medium which may furnish solutions to the energy crisis and contribute to establishing renewable energy structures [[2], [3], [4]]. It can directly produce or be upgraded into a variety of high-quality fuels including hydrogen (H2), carbon monoxide (CO), methanol, bio-oils, etc. Especially, FA is regarded as one of the most promising H2 storage materials with a remarkable volumetric capacity of ∼53.4 g/L, equivalent to 4.4 wt% of H2, which is close to the set value of 5.5 wt% by the US Department of Energy for efficient H2 storage substances. FA as the energy carrier is crucially beneficial for gaseous fuels to ease the storage and transportation in practical uses, and the dehydrogenation of FA into H2 has been extensively investigated which can be achieved in a simple, mild and easily-controlled manner. By manipulating the reaction parameters, FA can be alternatively decomposed into CO and therefore it is also a potential CO storage material. As a result, with its prevalent applications and outstanding virtues, FA is of principal significance to both the modern chemical societies and the energy industries (see Fig. 1).

FA naturally occurs in most ants, some species of bees, and in the atmosphere because of forest emissions. In fact, the name “formic” originates from Latin language formica which means ants because it was initially isolated by the distillation of ants. The current industrial production of FA involves a fossil-based, two-step method by first reacting methanol with CO to generate methyl formate which is then hydrolyzed to form FA (see Fig. 2, top). However, large-scale FA production from renewable resources are more preferable to mitigate carbon emission and fight against global warming, as part of a more sustainable human society [5]. So far, persistent endeavors have been made to obtain FA from renewable resources primarily the biomass or CO2 feedstock [[6], [7], [8], [9]]. Biomass grows based on photosynthesis utilizing solar energy with CO2 and water as the starting materials. Upon decomposition, the carbon emits back into the atmosphere to close the carbon cycle, in which no extra carbon is released. Biomass represents the largest carbon resource around the world and is considerably decent for chemical syntheses due to the inherently rich functionalities [[10], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22]]. Among the diverse types of biomass, cellulosic biomass with ample hydroxyl groups is inexpensive, readily available and the most abundant, which is therefore the most studied feedstock to produce FA by exploiting different transformation strategies.

Rather than treating it as a bothersome gas, CO2 itself can be regarded as a C1 building block chemical for the generation of a series of value-added chemicals and fuels such as FA [[23], [24], [25]]. This CO2-based refinery will help mitigate the carbon emission and simultaneously create economic values. Since CO2 is in the most oxidized state and relatively stable, highly active species or high energy inputs are usually necessary to reduce it, but the conditions can be modified by the rational design and development of catalysts. In fact, the reduction of CO2 into FA is relatively easier than to other products (methane, etc.) via hydrogenation, and the commonly used reducing agents include H2, water, etc. Notably, CO2 reduction into FA can be realized by chemocatalytic, photocatalytic and electrochemical methods. The reduction efficiency and selectivity are closely relevant to the surface chemistry, nanostructures, electronic states, etc. of the employed catalytic systems. In this review, renewable production of FA using biomass and CO2 as the feedstock will be the major focus (an overview is provided in Fig. 2, bottom). First, conversion of biomass (mainly cellulosic biomass) into FA by different transformation routes such as hydrolysis, wet oxidation, etc. is illustrated in detail. Next, recent advances in CO2 reduction into FA by chemical, photochemical and electrochemical methods will be emphasized along with the catalyst optimization tactics. Then, the applications of FA as an energy carrier to produce H2 will be briefly depicted to showcase its essential role in future hydrogen energy economy. Lastly, the challenges and prospects of renewable FA production will be discussed and summarized.

Section snippets

Acid hydrolysis of biomass

The conversion of glucose and cellulose under the catalysis of acids would lead to the simultaneous production of the value-added products levulinic acid (LeA) and FA [26]. It is generally recognized that in the presence of an acid, cellulose first undergoes hydrolysis to give oligosaccharides and glucose which are subsequently dehydrated into 5-hydroxymethylfurfural (5-HMF) via glucose isomerization, and then rehydration of 5-HMF happens to afford LeA and FA (see Fig. 3). Hence, in this

CO2 reduction into FA

The C1 chemistry based on CO2 as the feedstock has been increasingly attractive since it offers an appealing solution to both the carbon mitigation and the sustainable development of the society [[69], [70], [71]]. CO2 is a relatively stable compound and a reducing agent is indispensable for its utilization into fuels or chemicals [70,[72], [73], [74], [75], [76], [77]] which normally involve multiple electron-transfer processes. According to the calculated Gibbs energy, CO2 reduction to FA is

The dehydrogenation of FA to produce H2 fuel

A salient advantage and potential application of FA is its role as a H2 energy carrier to solve the storage issue for gas fuels, ease the transportation and improve the safety of using H2 as a fuel. The dehydrogenation of FA is a reverse reaction of CO2 hydrogenation, and many of the catalysts that catalyzed the CO2 hydrogenation into FA are also able to promote FA dehydrogenation. A common side reaction is the FA dehydration into water and CO which should be avoided to favor H2 fuel

Challenges and outlook

In the past decade, the conversion of biomass into FA has remarkably developed with prominent outcomes. The efficiency of the transformation is not any more a major challenge, and many of the catalytic systems can result in highly selective conversion of glucose into FA. Some works exploited powerful catalysts can even directly transform raw woody biomass such as waste paper into FA with relatively satisfactory yields. In particular, a room-temperature transformation strategy has been put

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This manuscript was supported by the Young Scientists Fund of the National Natural Science Foundation of China (No. 21908145), the Shanghai Sailing Program (19YF1422100) and the SJTU Global Strategic Partnership Fund (WF610561702).

References (162)

  • A.H. Chowdhury et al.

    Magnesium oxide as an efficient catalyst for CO2 fixation and N-formylation reactions under ambient conditions

    Mol. Catal.

    (2018)
  • F.C.F. Marcos et al.

    CuFe and CuCo supported on pillared clay as catalysts for CO2 hydrogenation into value-added products in one-step

    Mol. Catal.

    (2018)
  • Z. Srokol et al.

    Hydrothermal upgrading of biomass to biofuel; studies on some monosaccharide model compounds

    Carbohyd. Res.

    (2004)
  • A.T. Quitain et al.

    Low-molecular-weight carboxylic acids produced from hydrothermal treatment of organic wastes

    J. Hazard. Mater.

    (2002)
  • T. Bhaskar et al.

    Hydrothermal upgrading of wood biomass: influence of the addition of K2CO3 and cellulose/lignin ratio

    Fuel

    (2008)
  • K.V. Avramidou et al.

    Esterification of free fatty acids using acidic metal oxides and supported polyoxometalate (POM) catalysts

    Mol. Catal.

    (2017)
  • B.S. Rao et al.

    Selective conversion of furfuryl alcohol into butyl levulinate over zinc exchanged heteropoly tungstate supported on niobia catalysts

    Mol. Catal.

    (2017)
  • B. Yuan et al.

    A novel Brønsted-Lewis acidic catalyst based on heteropoly phosphotungstates: synthesis and catalysis in benzylation of p-xylene with benzyl alcohol

    Mol. Catal.

    (2017)
  • A.L.P. de Meireles et al.

    Heteropoly acid catalysts for the valorization of biorenewables: isomerization of caryophyllene oxide in green solvents

    Mol. Catal.

    (2018)
  • P.K. Kumari et al.

    Lewis acidity induced heteropoly tungustate catalysts for the synthesis of 5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural

    Mol. Catal.

    (2018)
  • S. Suganuma et al.

    Keggin-type molybdovanadophosphoric acids loaded on ZSM-5 zeolite as a bifunctional catalyst for oxidehydration of glycerol

    Mol. Catal.

    (2018)
  • B. Srinivasa Rao et al.

    One pot selective conversion of furfural to γ-valerolactone over zirconia containing heteropoly tungstate supported on β-zeolite catalyst

    Mol. Catal.

    (2019)
  • N.V. Gromov et al.

    Hydrolytic oxidation of cellulose to formic acid in the presence of Mo-VP heteropoly acid catalysts

    Catal. Today

    (2016)
  • J. Zhang et al.

    Catalytic oxidative conversion of cellulosic biomass to formic acid and acetic acid with exceptionally high yields

    Catal. Today

    (2014)
  • V. Jeyalakshmi et al.

    Metal oxides as photo catalysts: Modified sodium tantalate as catalyst for photo reduction of carbon dioxide

    Mol. Catal.

    (2018)
  • Y. Zhan et al.

    Biogas reforming of carbon dioxide to syngas production over Ni-Mg-Al catalysts

    Mol. Catal.

    (2017)
  • H. Wang et al.

    Non-thermal plasma enhanced dry reforming of CH4 with CO2 over activated carbon supported Ni catalysts

    Mol. Catal.

    (2019)
  • T. Zhao et al.

    Controllable preparation of ZIF-67 derived catalyst for CO2 methanation

    Mol. Catal.

    (2019)
  • J. Xu et al.

    NiO-MgO nanoparticles confined inside SiO2 frameworks to achieve highly catalytic performance for CO2 reforming of methane

    Mol. Catal.

    (2017)
  • M.S. Maru et al.

    Ruthenium-hydrotalcite (Ru-HT) as an effective heterogeneous catalyst for the selective hydrogenation of CO2 to formic acid

    Mol. Catal.

    (2018)
  • K. Singh Rawat et al.

    Metal-ligand bifunctional based Mn-catalysts for CO2 hydrogenation reaction

    Mol. Catal.

    (2019)
  • P.G. Jessop et al.

    Recent advances in the homogeneous hydrogenation of carbon dioxide

    Coord. Chem. Rev.

    (2004)
  • S. Kar et al.

    Advances in catalytic homogeneous hydrogenation of carbon dioxide to methanol

    J. CO2 Util.

    (2018)
  • N. Yan et al.

    Transformation of CO2 by using nanoscale metal catalysts: cases studies on the formation of formic acid and dimethylether

    Curr. Opin. Chem. Eng.

    (2018)
  • G.A. Filonenko et al.

    On the activity of supported Au catalysts in the liquid phase hydrogenation of CO2 to formates

    J. Catal.

    (2016)
  • M.S. Maru et al.

    Ruthenium-hydrotalcite (Ru-HT) as an effective heterogeneous catalyst for the selective hydrogenation of CO2 to formic acid

    Mol. Catal.

    (2018)
  • D.A. Bulushev et al.

    Towards sustainable production of formic acid

    ChemSusChem

    (2018)
  • W. Supronowicz et al.

    Formic acid: a future bridge between the power and chemical industries

    Green Chem.

    (2015)
  • K. Sordakis et al.

    Homogeneous catalysis for sustainable hydrogen storage in formic acid and alcohols

    Chem. Rev.

    (2018)
  • J.T. Overpeck et al.

    A call to climate action

    Science

    (2019)
  • M. Mikkelsen et al.

    The teraton challenge. A review of fixation and transformation of carbon dioxide

    Energy Environ. Sci.

    (2010)
  • S.C. Roy et al.

    Toward solar fuels: photocatalytic conversion of carbon dioxide to hydrocarbons

    ACS Nano

    (2010)
  • D.A. Bulushev et al.

    Heterogeneous catalysts for hydrogenation of CO2 and bicarbonates to formic acid and formates

    Catal. Rev.

    (2018)
  • F. Valentini et al.

    Formic acid, a biomass-derived source of energy and hydrogen for biomass upgrading

    Energy Environ. Sci.

    (2019)
  • X. Chen et al.

    Base-catalysed, one-step mechanochemical conversion of chitin and shrimp shells into low molecular weight chitosan

    Green Chem.

    (2017)
  • X. Gao et al.

    Transformation of chitin and waste shrimp shells into acetic acid and pyrrole

    ACS Sustain. Chem. Eng.

    (2016)
  • X. Chen et al.

    One-step synthesis of N-heterocyclic compounds from carbohydrates over tungsten-based catalysts

    ACS Sustain. Chem. Eng.

    (2017)
  • N. Yan et al.

    Sustainability: don’t waste seafood waste

    Nature

    (2015)
  • X. Chen et al.

    Shell biorefinery: dream or reality?

    Chem. Eur. J.

    (2016)
  • T. Flannelly et al.

    Non-stoichiometric formation of formic and levulinic acids from the hydrolysis of biomass derived hexose carbohydrates

    RSC Adv.

    (2016)
  • Cited by (0)

    View full text