Version of Record: https://www.sciencedirect.

com/science/article/pii/S0920586118316572
Manuscript_b0ed0e9d7a9f05c5308ec858c405f9c8
1- Catalysis Today

CO2 Methanation Under Dynamic Operational

Mode Using Nickel Nanoparticles Decorated Carbon
Felt (Ni/OCF) Combined with Inductive Heating

Wei Wang,a,* Cuong Duong-Viet,a,b Zhenxin Xu,a Housseinou Ba,a Giulia Tuci,c,d
Giuliano Giambastiani,a,c,* Yuefeng Liu,e Tri Truong-Huu,f Jean-Mario Nhut,a
Cuong Pham-Huua,*

a
Institute of Chemistry and Processes for Energy, Environmental and Health (ICPEES),
ECPM, UMR 7515 of the CNRS-University of Strasbourg, 25 rue Becquerel, 67087
Strasbourg Cedex 02, France
b
Ha-Noi University of Mining and Geology, 18 Pho Vien, Duc Thang, Bac Tu Liem, Ha-Noi,
Vietnam
c
Institute of Chemistry of OrganoMetallic Compounds, ICCOM-CNR and Consorzio INSTM,
Via Madonna del Piano, 10 – 50019, Sesto F.no, Florence, Italy
d
Department of Chemistry “Ugo Schiff”, University of Florence, 50019, Sesto Fiorentino, Italy
e
Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics,
Chinese Academy of Science,457 Zhongshan Road, 116023 Dalian, China
f
The University of Da-Nang, University of Science and Technology, 54, Nguyen Luong Bang,
Da-Nang, Viet-Nam

Corresponding authors:
[email protected] (W. Wang)
[email protected] (G. Giambastiani)
[email protected] (C. Pham-Huu)

1
© 2019 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
 2- Catalysis Today

Abstract

Carbon dioxide (CO2) hydrogenation to methane (CH4) (Sabatier reaction) is a

fundamental process that meets with several key challenges of our modern society. Besides

representing a convenient way to the metal-mediated conversion of a natural and abundant

“waste” into a fuel of added value, its combination with H2 from renewable resources (REs)

represents a challenging technology for the REs storage. In addition, its practical exploitation

can give a concrete answer to many critical societal and environmental issues largely related to

the steadily increase of CO2 concentration in the Earth’s atmosphere caused by the main

anthropic activities. Although many fundamental achievements have also been reached since

its discovery at the beginning of the twentieth century, alternative and conceptually new

protocols for the process can provide valuable solutions to the optimization of the catalyst

performance, process energetics and catalyst life-time on stream.

This contribution describes the synthesis of an efficient and robust catalyst for the CO2

methanation, based on Nickel nanoparticles (Ni-NPs) grown on electrically conductive and

macroscopically shaped oxidized carbon-felt disks (OCF), heated at the target reaction

temperature by electromagnetic induction. At odds with the more classical external heat sources

(based on contact heat conduction), induction heating allows the electromagnetic energy to be

directly absorbed by the susceptor (OCF) who converts it into heat to be transferred to the

catalyst active sites (Ni NPs). Inductive heating (IH) of Ni/OCF gives CO2 conversion (XCO2)

up to 74% and CH4 selectivity (SCH4) close to 97% already at 320 °C, showing an excellent

control of the catalyst stability under forced dynamic operational conditions.

Keywords: CO2 methanation; Inductive heating; Oxidized carbon felt; Nickel nanoparticles;
Synthetic natural gas

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1. Introduction

The restless development of renewable energy sources (REs), i.e. solar and wind, calls

for the development of more efficient energy storage systems capable to cope with problems

related to the extra and intermittent renewable energy supply. Indeed, the fluctuating nature of

REs has to be taken into account while managing electricity grids in order to reduce problems

linked to security and stability of power networks and ensure a constant supply of electricity on

demand [1-3]. Apart from electrochemical storage devices, i.e. supercapacitors and batteries,

chemical energy storage is a fast growing technology that allows the conversion of exceeding

electricity from REs into H2 (by water electrolysis) [4-6]. The latter is supposed to be used in

turn as an energy vector or an intermediate for the production of chemicals and commodities.

On this regard, CO2 hydrogenation [7-10] (Sabatier reaction) using H2 from RE sources [11,

12] is a highly promising approach that meets with several key challenges of our modern

society. Besides representing a sustainable method towards the production of chemicals and

fuels [13-20] from REs it also copes with the main environmental and climate urgencies directly

linked to steadily state increase of CO2 concentration in the atmosphere. Catalytic

hydrogenation of CO2 with RE H2 is nowadays at the forefront of many chemical technologies

devoted to the production of low molecular weight olefins [21], hydrocarbons [22], formic acid

[23], and alcohols [24-26]. It also represents the core business of the ‘‘power to gas’’ (PtG)

technology [5, 6, 27-29]. Indeed, it provides a powerful approach to the production of synthetic

natural gas (SNG) as fuel (CO2 methanation) that can be injected in the existing natural gas

pipelines thus creating a virtuous link between existing power networks and natural gas grids

[30]. CO2 methanation is a well-established transformation promoted by a relatively large

number of metal active phases [i.e. Ni, Ru, Rh, Co, Pd nanoparticles (NPs)] deposited on

various oxide supports (i.e. TiO2, SiO2, Al2O3, CeO2, MgO and ZrO2) [31-40]. It is a highly

exothermic process (∆H = -165 kJ mol-1) and thus, thermal conductive supports (carbon

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nanotubes, graphene, and silicon carbide just to mention a few) [41-45] are generally

recommended in order to prevent as much as possible the generation of local temperature

gradients (hot spots) inside the catalyst bed during the process. Indeed, the generation of “hot

spots” inside the catalyst can be largely detrimental both in terms of catalyst life-time and

performance of the methanation process.

PtG chain urgently needs of novel concepts and breakthroughs to optimize performance

of existing plants and to cope as much as possible with dynamic operational conditions that

often occur within the reactor. One main dynamic parameter to be controlled is represented by

the intermittent nature of reactants supply from REs. Such dynamic conditions can be

responsible for the occurrence of severe temperature fluctuations within the reactor, not easy to

be controlled even in apparatus equipped with external cooling systems [46].

Induction heating (IH) represents a valid alternative to the more traditional Joule heating

(JH) approach, with the former listing a series of key advantages compared to the latter in the

heating of electrically conductive materials. Induction heating is likely a cleaner, efficient, cost-

effective, precise and repeatable method for providing heat necessary for chemical processes to

occur. Heating takes place on electrically conductive objects when they are placed in a varying

magnetic field and it occurs precisely where heat is needed and not to the whole volume of the

medium and the gaseous reactants; it is also defined as a noncontact heating method. Such a

heating scheme allows for rapid up/down temperature ramps (i.e. hundred degrees per minute),

with great potentials for large scale and rapid manufacturing processes and improved energy

efficiencies [47].

IH is expected to be a technique of choice for operating heterogeneous catalysis and in

particular for those processes where high heat targeting along with fast heating/cooling rate

provide key control on the reaction course and catalyst stability on stream, i.e. rapid temperature

gradient control during exothermic or endothermic processes also caused by variable reagents

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loads. Most importantly, the temperature control at the catalyst sites can be directly monitored

by a laser pyrometer that maps the catalyst temperature in real time (and not that of the reactor)

thus allowing an extremely fast response to any temperature deviation occurring at the catalyst

bed. By this way, the catalyst operates under almost isothermal conditions.

IH has already been used with success for running liquid-phase catalytic reactions [48,

49] and recently for the gas-phase CO2 methanation reaction. On the latter process, Bordet et

al. [50] have elegantly demonstrated the use of the induction heating with Ni-coated iron-

carbide NPs (ICNPs@Ni) or ICNPs supported on Ru-doped Silica-alumina hydrate oxides

(SIRALox) as catalysts for continuous-flow reactors working under atmospheric pressure. For

both their systems, the authors idea was to take advantage of ICNPs heating capacities and

transfer the heat released from that NPs to activate either their Ni-coating or the neighbouring

Ru NPs, thus catalysing the Sabatier process.

In this work we describe the straightforward synthesis of Ni(0) NPs on a highly defective

carbon felt (Ni/OCF) support and the use of the composite as a stable and effective

heterogeneous catalyst for CO2 methanation, using an induction heating (IH) setup. We took

advantage from the high and rapid heat response (heating/cooling) of OCF to magnetic stimuli

of the inductive heater for a rapid temperature control at the heart of the catalytic system. Such

a configuration provides an effective way to control the catalyst temperature from sudden

deviations especially occurring during the start/stop of the catalytic runs where gradients of

reactants loads can be formed.

2. Experimental Section

2.1. Materials and methods.

Commercial soft polyacrylonitrile (PAN)-based carbon felt (CF) was purchased from

Carbone Lorraine Ltd. [RVC 4002 Carbon felt (d = 100 kg m-3; 96% carbon content; Specific

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Surface Area (SSA): 2.0 ± 1 m2 g-1] in the form of a black carpet with a thickness of 12 mm. It

can be easily adapted into various macroscopic shapes including cylinders, disks or others as a

function of its downstream application. The as-received CF sample was cut into disks of

external diameter of 22 mm before being oxidized upon treatment with gaseous nitric acid (68

wt.% HNO3) [51]. In a typical oxidation procedure, CF disk is located inside a tubular quartz

reactor heated to 250 oC by an external electrical furnace. Nitric acid vapors obtained by heating

concentrated nitric acid (68 wt.% HNO3) at 125 °C were then allowed to pass through the

tubular reactor for 4 h. Afterwards, the oxidized carbon felt (OCF) was thoroughly washed with

distilled water and dried in an oven at 110 oC to constant weight prior any use (Fig. S1 and

Table S1).

Nickel NPs were deposited on OCF by incipient wetness impregnation [52], using an

aqueous solution of nickel nitrate [Ni(NO3)2·6H2O] as to get a theoretical metal loading close

to 10 wt.%. The oven-dried pre-catalyst was calcined in air at 200 °C for 1 h as to convert the

nickel nitrate into its oxide counterpart. Afterwards, NiOX/OCF underwent a reduction step at

350 °C for 1 h under a dynamic stream of H2 (100 mL min-1). Nickel loading was fixed by

Inductively Coupled Plasma Atomic Emission spectrophotometry (ICP-AES) after complete

acidic mineralization of NiOX/OCF sample, using an Optima 2000 Perkin Elmer Inductively

Coupled Plasma (ICP) Dual Vision instrument; the effective nickel charge was then fixed to

8.4 wt.%. Scanning electron microscopy (SEM) was conducted on a ZEISS GeminiSEM 500

microscope with a resolution of 5 nm. For each measurement, samples were deposited onto a

double face graphite tape in order to avoid charging effect during the analysis. Transmission

Electron Microscopy (TEM) was carried out on a JEOL 2100F microscope working at 200 kV

accelerated voltage, equipped with a probe corrector for spherical aberrations, and a point-to-

point resolution of 0.2 nm. For these measurements, samples were previously dispersed in

ethanol using ultrasounds (for few minutes) till a homogeneous dispersion is obtained and the

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resulting inks are drop-casted on a copper grid covered with a holey carbon membrane. The

Brunauer-Emmett-Teller (BET) specific surface areas (SSA) and porosity (Based on BJH

method) were calculated from N2 physisorption isotherms recorded at 77 K on an ASAP 2020

Micromeritics® instrument. All samples were degassed/activated at T = 250 °C for 8 h prior

their characterization. Thermal gravimetric analysis (TGA) and differential thermal

gravimetric (DTG) analysis were run in the 50 - 800 °C temperature range (heating rate of 5 °C

min-1) using a TGA Q5000 instrument operating under an air flow (25 mL min-1). Inductive

heater and laser (still missing details).

2.2. CO2 methanation process

The CO2 methanation reaction (Eq. 1) was carried out under atmospheric pressure in a

fixed-bed quartz tubular reactor [Ø(ID) 20 mm, length of 600 mm] charged with the disk pre-

catalyst (NiOX/OCF) and equipped with an advanced EASYHEAT induction heating system

for the precise control of the reaction temperature in the 200 - 380 °C range. Prior of each

experiment, the calcinated NiOX/OCF pre-catalyst was reduced at 350 °C for 1 h under a stream

of H2 (100 mL min-1). The applied conditions to the NiOx reduction to Ni(0) were monitored

by XRD analysis of the pre-catalyst before and after reduction treatment (see Fig. S2). Finally,

CO2 and H2 were fed into the reactor with a well-defined molar ratio by a series of calibrated

Mass Flow Controllers (Brookhorst®). For comparative CO2 methanation trials carried out

using a classical external heater (JH), the quartz tube reactor containing Ni/OCF was housed

inside an electric furnace controlled by a thermocouple for the monitoring of the temperature

ramp and equipped with a second temperature controller placed in contact with the catalyst bed.

In a typical run, a 4 v/v ratio H2-to-CO2 gas mixture was admitted at the top of the reactor

and passed downward through the catalytic disk. Gases at the reactor outlet are passed through

a trap filled with silicon carbide pellets where traces of water are condensed before reaching

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the gas chromatograph. Reactants and products were analyzed on-line by a CP-3800 gas

chromatograph (GC) equipped with a thermal conductivity (TCD) and flame ionization (FID)

detectors. All exit lines were maintained at 110 °C by heating tapes to avoid condensation of

water remained in the feed.

CO2 + 4 H2 → CH4 + 2 H2O ∆H = -165 kJ mol-1 (Eq. 1)

CO2 conversion (XCO2) and CH4 selectivity (SCH4) were calculated according to the

following equations (Eq. 2 and 3):

FCO 2 (in ) − FCO 2 (out )

CO2 conversion: X CO (%) = x100 (Eq. 2)
2
FCO 2 (in )

FCH 4 (out )
CH4 selectivity: SCH 4 (%) = x100 (Eq. 3)
FCH 4 (out ) + FCO (out )

Where FCO 2 (in ) (mL min-1) is the volume of CO2 admitted to the reactor and FCO2 (out) (mL

min-1) is the volume of CO2 measured at the reactor outlet. This latter was calculated using the

total volume at the reactor outlet and considering the percentage of CO2 detected by GC

analysis. The CH4 selectivity (SCH4) was calculated by GC analysis of the recovered flow at the

reactor outlet where CO was detected as the unique reaction by-product.

For the present CO2 methanation study, catalyst underwent a series of successive start

and shut-down steps as to simulate the dynamic operation conditions of a CO2 methanation

plant as a consequence of the intermittent nature in reactants supply. To this aim, the start/stop

process was operated as follows: at the steady-state (320 °C) the reaction temperature was

decreased to 260 °C and the reactants flow was replaced by helium for 15 minutes before raising

rapidly again the reaction temperature to 320 °C (or 340 °C) and re-start the reactants flow

supply. Such start/stop sequences are repeated several times in order to evaluate all possible

deactivation/alteration effects occurring on Ni/OCF.

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2.3. Induction Heating Setup

The induction heating setup (EasyHeat LI) was purchased from Ambrell Ltd. (The

Netherlands). It consists in a spiral 5-turn induction coil internally cooled with recirculated

water (10% glycerol) provided by an external chiller. The quartz reactor containing the catalyst

is placed inside induction heater coils as shown in Fig. 1. Temperature regulation was ensured

by a PID system (Eurotherm model 3504) connected to a laser pyrometer (Optris®, Germany,

Fig. 1) working in the 150 - 1000 °C temperature range (accuracy at ambient temperature 23 ±

5°C), for the real-time control of the temperature inside the catalyst bed. The heating/cooling

rate allowed for the system is in the order of c.a. 200 oC min-1.

Fig. 1. Digital photos of the Ni/OCF catalyst in the quartz tubular reactor placed inside the coils
of the inductive heater along with the laser pyrometer for the control of the temperature inside
the catalyst bed.

3. Results and Discussion

3.1. Ni/OCF catalyst synthesis and characterization

The acid treatment of CF is used to confer a hydrophilic character to the pristine

hydrophobic material as to get a more wettable surface for the impregnation step with an

aqueous solution of [Ni(NO3)2·6H2O]. Although such an acid treatment deeply contributes to

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the modulation of the chemico-physical properties (vide infra) of the CF surface, it negligibly

affects the sample’s macroscopic shape. Accordingly, the catalyst shape can be fixed at priori

on the pristine CF as a function of its final downstream application (Fig. 2A). SEM and TEM

micrographs of OCF at different magnifications show a composition made of carbon

microfilaments with an average diameter of 10 ± 1 µm, featured by a highly defective and low

structured C-surface morphology (Fig. 2B-E). Indeed, the initial oxidation treatment with

HNO3 vapors is supposed to deeply modify the CF surface properties in terms of chemical

composition (i.e. formation of oxygenated functional groups on highly defective C-atoms) [51],

specific surface area (SSA) and pore-size distribution (vide infra).

Fig. 2. (A) Examples of macroscopic shapes available for potential applications. (B) SEM
micrograph of CF. (C to E) Representative SEM and TEM micrographs of the OCF sample
after acid treatment showing the formation of disordered carbon structure at the outer material
surface.
TGA/DTG profiles of CF samples before and after acid treatment are outlined in Fig. 3A.

OCF displays a significant decrease of the oxidation temperature compared to its pristine

counterpart. This trend is in line with the presence on OCF of a reduced degree of structured

carbons [51, 53]. Most importantly, the oxidative treatment translates in a significant change of

the material specific surface area (SSA) that increases from about 2 (CF) to 689 m2 g-1 (OCF)

(Fig. 3B and Table 1). After OCF impregnation with a solution of [Ni(NO3)2·6H2O] and

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calcination, the SSA of the composite is reduced down to 463 m2 g-1 in line with a modification

of the material morphology as a consequence of the calcination treatment and the partial pore

clogging caused by the NiOX NPs deposition (Fig. 3B and Table 1).

Fig. 3. (A) TGA/DTG profiles of the CF and OCF recorded under an oxidative flow (O2/He :
20/80 v/v%, 50 mL min-1) in the 50 - 850 °C temperature range with a heating rate of 5 °C min-
1
. (B) N2 adsorption-desorption isotherms of OCF and NiOX/OCF samples.

Table 1. Specific surface area (SSA), total and

micropore volume of CF samples and composites.
SSAa Vp(total)b Vp(micro)c
Sample
[m2 g-1] [cm3 g-1] [cm3 g-1] (%)d
CF ≈2 0.004 n.d.
OCF 689 0.26 0.038 (14.6%)
NiOx/OCF 463 0.45 0.037 (8.2%)
a
Brunauer–Emmett–Teller (BET) specific surface area (SSA)
measured at T = 77 K; b Total pore volume determined by using
the adsorption branch of N2 isotherm at p/p0 = 0.98; c Micropore
volume calculated by t-Plot method. d % of micropore volume
over Vp(total)

Both samples (OCF and NiOX/OCF) exhibit a Type IV isotherm with a moderate but

distinctive (for OCF in particular) H4 hysteresis loop in the range of 0.4 – 1.0 p/p0, typical of

mesoporous structures featured by complex pore networks of ill-defined shape [54].

The NP distribution on the Ni/OCF catalyst, after calcination/reduction, was analyzed by

Transmission Electron Microscopy (TEM) and representative images of the sample at different

magnifications are given in Fig. 4 (A, B). TEM micrographs reveal a roughly monodisperse

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and dense distribution of Ni NPs all over the sample with an average particle size of about 4 ±

1 nm, as determined from a statistical TEM analysis over 200 particles. The relatively narrow

Ni NPs dispersion on OCF can be ascribed to a non-innocent role played by the oxidized

nanocarrier. Indeed, relatively strong interactions between the Ni salt precursor and the highly

defective and hydrophilic OCF surface are thought to be crucial for limiting NPs agglomeration

phenomena throughout all thermal phases the composite undergoes.

Fig. 4. (A, B) Low and medium magnification TEM micrographs of Ni/OCF. Histogram refers
to the particle size distribution as measured over 200 NPs.

3.2 CO2 methanation trials with Ni/OCF as catalyst using inductive heating.

3.2.1 The influence of the reaction temperature

In a typical methanation run, a disk of NiO/OCF catalyst is fixed in a quartz tubular

reactor, housed inside the inductor heating coils and pre-treated for 1 h at 350 °C under a stream

of pure H2 (see Experimental Section for details). Afterwards, the temperature of the reduced

Ni/OCF catalyst is fixed at the desired target value and a H2/CO2 mixture (4 v/v ratio) is

introduced downward through the catalyst bed at ambient pressure (1 atm) and at a GHSV of

30,000 mL gcat-1 h-1. CO2 conversion (XCO2) and methane selectivity (SCH4) measured in the 160

- 380 °C temperature range are outlined in Fig. 5. According to literature precedents, XCO2

steadily increases while increasing the reactor temperature and it rapidly approaches conversion

values close to those at the thermodynamic equilibrium (Fig. S3) [55-57]. Noteworthy, Ni/OCF

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offers excellent performance already at moderately high temperature values. Indeed, it reaches

a XCO2 up to 74% with a SCH4 close to 97% at 320 °C under the same experimental conditions

mentioned above (H2/CO2 = 4 v/v ratio; GHSV = 30,000 mL gcat-1 h-1). This result is even more

relevant if we consider that Ni/OCF operates under more severe reaction conditions compared

to many other systems reported so far, using pure reactants flows with no need of their dilution

by any inert carrier.

CO represents the unique reduction intermediate for the process detected along with CH4

at the reactor outlet. For methanation trials at temperatures < 300 °C, SCH4 is rather moderate

because of the kinetic stability of CO that makes its conversion into CH4 hard to be

accomplished under these conditions. At higher temperatures, (i.e. > 320 °C) both XCO2 and

SCH4 decrease mainly as a consequence of side processes at work i.e. steam reforming (< SCH4),

water-gas shift (< XCO2) or reverse water-gas shift reactions (< SCH4) [58].

For the sake of comparison with a more traditional external heating system (Joule heater

- JH), the methanation process was repeated on a new batch of Ni/OCF under the same catalytic

conditions operated above except for the use of an electrical furnace for the set-up of the target

reaction temperature. Accordingly, the reactor containing the reduced Ni/OCF catalyst was

housed inside the electric furnace equipped with a thermocouple for the monitoring the

temperature ramp and with a second temperature controller placed in contact with the catalyst

bed. Under these conditions, Ni/OCF performance changes significantly with a XCO2 that is

reduced down by a factor of 57% (at 320 °C) respect to the value measured under IH at the

same temperature (XCO2IH and XCO2JH at 320 °C are 74% and 32%, respectively; Fig. 5).

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Fig. 5. CO2 methanation runs with Ni/OCF as catalyst [CO2 conversion (XCO2: ̵ ̵ ) and CH4
selectivity (SCH4: ̵ ̵ )], operated by an induction heating (IH) setup. Green spheres refer to CO2
conversion (XCO2: ̵ ̵ ) measured with a classical Joule heating system. Temperatures refer for
both heating methods to those directly measured at the catalyst bed. Reaction conditions:
catalyst weight = 0.23 g (8.4 wt.% of Ni), GHSV (STP) = 30,000 mL gcat-1h-1), [CO2] = 20%,
[H2] = 80%, H2-to-CO2 v/v ratio = 4. Calculated resident time on catalyst: 1.2 s.

Noteworthy, under JH conditions, Ni/OCF catalyst reaches a XCO2 value of 65% (SCH4 =

92.5% - see Fig. S4) only after increasing the reactor temperature over 380 °C. Such a result

can be ascribed to the effectiveness of the induction heating approach that supplies the heat

necessary for the process directly to the catalyst. Besides providing a precise and easily tuning

temperature control at the catalyst bed throughout the reaction process, IH largely prevents heat

losses mainly due to conduction and convection phenomena typical of contact heating modes

(i.e. JH). This aspect is crucial for many industrial processes where limited catalyst performance

is often due to physical constraints related to an effective heat transfer to the catalyst rather than

to the inherent catalyst activity. Rostrup-Nielsen and co-workers [59] have calculated that only

10% (or even less) of the external heating provided to reformer tubes is employed in the

catalytic process, while the (large) remaining part is dissipated by heat transfer restrictions

encountered in contact heating modes from the heat source to the catalyst. Recently, Vinum et

al. [60] have described the use of dual-function Co–Ni NPs in combination with the induction

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heating as unique energy source for operating steam methane reforming (SMR). At odds with

more classical heating supply systems, the authors have concluded that under IH the catalyst

operates at its kinetic limit; i.e. the catalyst performance is limited by the reaction kinetic and

not by the heat transfer.

Influence of dynamic operational modes on Ni/OCF. As a model trial for testing Ni/OCF

under dynamic conditions, successive start/stop process cycles have been investigated while

keeping the catalyst under variable reaction temperatures, GHSVs and using pure reactants as

reaction feed. These trials are made possible due to the fine and almost instantaneous catalyst

temperature control within the processes operated under induction heating. Indeed, heating and

cooling rates with IH are extremely fast (i.e. ≥ 200°C min-1) and they can be easily controlled

avoiding sudden and detrimental temperature deviations on the catalyst at work. A complete

overview of several start/stop CO2 methanation cycles carried out with Ni/OCF under variable

conditions (temperature and GHSV) is presented on Fig. 6.

According to the catalytic outcomes (XCO2 and SCH4), successive start/stop cycles

consisting in a rapid catalyst cooling/heating in the 260 - 320 °C temperature range and

simultaneous replacement of the H2/CO2 feed with Helium, do not show any appreciable

modification of the catalyst performance even after several cycles. Noteworthy, such start/stop

tests cannot be run under conventional heating mode (i.e. JH) because of longer induction times

required during the cooling and heating phases. Moreover, fast heating/cooling rates along with

a fine control of the target temperature at the catalyst bed provide the reactor with a powerful

tool for the control (almost in real time) of those phenomena related to the discontinuous supply

of reagents into the reactor.

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Fig. 6. Ni/OCF catalyst performance miming dynamic operational condition modes in the form
of successive start/stop cycles operated under different conditions (temperature and GHSV).
Reaction conditions: catalyst weight = 0.23 g, GHSV (STP) = 30,000 or 60,000 mL gcat-1 h-1;
H2-to-CO2 = 4 v/v ratio; operative reaction temperatures and times: 320 °C or 340 °C for 1 h;
hold-on temperature value for the shut-down period: 260 °C for 0.25 h.

Indeed, a fine and fast temperature control is crucial to avoid sudden temperature raises

at the catalyst bed, thus limiting detrimental effects for the catalyst (i.e. decomposition and/or

NPs sintering) and the catalytic process. Besides the role played by the support thermal

conductivity, the generation of local temperature gradients (“hot spots”) inside the catalyst can

be conveniently balanced by the high heating/cooling rates operated with the IH system. It is

known that local temperature gradients at the catalyst bed can be generated in the CO2

methanation even within reactors operating at low GHSVs and using reagent feeds diluted with

inert carriers [45]. Accordingly, their generation can have even more drastic effects in reactors

working at higher GHSV and fed with pure reactants flows. In the CO2 methanation with

Ni/OCF operated by IH, the combination of the temperature control inside the catalyst (ensured

by IH mode) together with the medium thermal conductivity of the OCF support, provide a

robust and effective system for the process where the generation of local “hot spots” is largely

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prevented if not totally suppressed. This key feature well matches with the high catalyst stability

under the discontinuous (start/stop) and dynamic (temperature and GHSVs) operational modes

described above for the Sabatier reaction. As an additional proof of the Ni/OCF stability on

stream, long-term evaluation tests have been properly addressed under constant reaction

conditions.

Long-term stability evaluation tests. The stability of Ni/OCF to perform CO2 methanation

efficiently has also been investigated as a function of the catalyst time on stream and results are

presented on Fig. 7. Ni/OCF displays a high and stable CO2 conversion (XCO2) for more than

80 h on stream thus indicating that deactivation phenomena (i.e. active phase sintering, metal-

nanoparticles passivation by coke deposits or metal leaching) are unlikely to occur under these

conditions. Wei and co-workers [61] have recently shown how unpromoted Ni NPs decorated

carbon nanotubes (Ni/CNTs) as a catalyst for the CO2 methanation, gradually deactivates over

time on stream, mainly due to the generation of coke deposits.

Fig. 7. Long-term evaluation tests with Ni/OCF as CO2 methanation catalyst. Reaction
conditions: catalyst weight = 0.23 g, GHSV (STP) = 30,000 mL gcat-1 h-1; H2/CO2 = 4 v/v ratio;
reaction temperature = 320 oC.

Feng [43], Centi [62] and Stangeland [55] have also described Ni-based catalysts for the

process, using different alumina or promoted supports. Examples from this series show that

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catalyst deactivation can also take place through Ni NPs sintering induced by the local

generation of temperature gradients that progressively reduce the number of available active

sites.

TEM analysis of the exhaust Ni/OCF catalyst (Fig. 8A-B) is used to unveil the stability

of the composite on stream. A comparative analysis of Ni NPs on the exhaust catalyst (after

more than 80 h on stream) with those of its freshly prepared counterpart (see Fig. 4A-B) shows

only a moderate NPs sintering.

Fig. 8. (A, B) Low and medium magnification TEM micrographs of the exhaust Ni/OCF
catalyst after long-term evaluation test (> 80 h). Reaction conditions: catalyst weight = 0.23 g,
GHSV (STP) = 30,000 mL gcat-1 h-1; H2/CO2 = 4 v/v ratio; reaction temperature = 320 oC.
catalytic evaluation. Histogram refers to the particle size distribution as measured over 200
NPs.
TEM micrographs show that exhaust catalyst maintains a similar dispersion and

distribution of Ni NPs than its pristine counterpart with an average particle size distribution of

about 5 ± 1 nm (determined from a statistical analysis over 200 particles) and the absence of

any macro-aggregate all over the scanned area. Such a high thermal resistance of Ni NPs

throughout the whole catalytic run is also ascribed to the existence of relatively strong

interactions engaged between NPs and the highly defective OCF support.

These evidences indirectly confirm the excellent thermal control at the catalyst active

phase ensured by IH and the OCF thermal conductivity. Both of features have largely beneficial

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effects on the catalyst stability, in particular with respect to the control on the generation of

local temperature gradients that can easily start NPs sintering phenomena.

4. Conclusions

In summary, an efficient and robust catalyst for the CO2 methanation, based on Nickel

nanoparticles (Ni-NPs, 8.4 wt.%) grown on electrically conductive and macroscopically shaped

oxidized carbon-felt disks (OCF), has been prepared and heated at the target reaction

temperature by electromagnetic induction. Inductive heating (IH) is proved to have largely

beneficial effects on the catalyst performance compared to the more classical Joule heating

methods. Indeed, the electromagnetic energy provided by the induction heater can be directly

absorbed by the electrically conductive susceptor[63] (OCF) who converts it into heat to be

transferred to Ni NPs. By this way, an almost real-time control of the target temperature at the

catalyst active sites can be set-up with valuable advantages in terms of process energetics,

catalyst efficiency and catalyst stability on stream. Indeed, the fast temperature regulation rate

(hundreds of °C per min) ensured by IH, can control and balance undesired and sudden

temperature changes at the catalyst bed. As a matter of fact, temperature fluctuation at the

catalyst bed, frequently encountered in real systems (as the consequence of a discontinuous

supply of reagents loads), can be finely controlled thus allowing the reactor to operate under

virtually isothermal conditions. Inductive heating (IH) of Ni/OCF gives CO2 conversion (XCO2)

up to 74% and CH4 selectivity (SCH4) close to 97% already at 320 °C using pure reactants flows

with no need of their dilution by any inert carrier. Noteworthy, the same catalyst under a more

conventional JH control, reaches XCO2 value of 65% and SCH4 of 92.5% for a reactor

temperature set-up to 380 °C.

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Ni/OCF has also shown an excellent stability upon IH when forced dynamic operational

conditions are applied (reaction temperature, GHSV and reagents loads). In a model trial,

dynamic operational modes have been expressly forced in the system as to mimic the process

discontinuity under conditions close to those operated in real plant. Accordingly, several and

sequential start/stop cycles have been run, including changes in the target reaction temperature

and GHSV, thus unveiling the extremely high stability of Ni/OCF under harsh experimental

conditions. Finally, a long-term experiment (> 80 h) has been used to confirm the stability of

the catalyst after several hours on stream. TEM analyses of the exhaust Ni/OCF have been

finally used to rule out the occurrence of any appreciable NPs sintering throughout the process.

Moreover, NPs passivation by the generation of coke deposits seems to be unlikely to occur

due to the efficient heat management within the process ensured by IH. Studies on Ni/OCF in

CO2 methanation under more severe reaction conditions are currently ongoing in our labs and

will be reported soon elsewhere.

Acknowledgements

G. G. and C. P.-H. thank the TRAINER project (Catalysts for Transition to Renewable

Energy Future) of the “Make our Planet Great Again” program (Ref. ANR-17-MPGA-0017)

for support. The Italian team would also like to thank the Italian MIUR through the PRIN 2015

Project SMARTNESS (2015K7FZLH) “Solar driven chemistry: new materials for photo- and

electrocatalysis” for financial support to this work. W. W. and Z. X. would like to thank the

China Scholarship Council (CSC) for financial support during his Ph.D. stay at the ICPEES.

SEM analysis was carried out at the joint SEM platform of the ICPEES-IPCMS and T. Romero

(ICPEES) is gratefully acknowledged for performing experiments. Dalian Institute of Chemical

Physics (DICP, Dalian, China) is also acknowledge for providing access to its TEM facilities.

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TOC graphic

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