Research Summary

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BIOGRAPHICAL INFORMATION

B.Sc., MSc. Chemical Engineering (1984); University of Mining and Metallurgy, Krakow, Poland; Department of Coal Processing in Power Engineering Chemistry.

Ph.D. Chemical Engineering/Materials Science (1989); Technical University of Krakow, Poland; Department of Chemical Engineering and Technology.

D.Sc. (habilitacion) Analytical Chemistry/Physical Chemistry (1998). M. Curie-Sklodowska University, Lublin, Poland.

HONORS AND AWARDS

1.        Appointed to National Academies Committee On Examination of the Disposal of Activated Carbon from the Heating, Ventilation and Air Condition Systems at Chemical Agent Disposal Facilities (May 2008- May 2009).

2.       On the Editorial Board of Adsorption Science and Technology (2005-present)

3.       On the Editorial Board of Journal of Colloid and Interface Science (2008-2010)

4.       On The Advisory Board of American Carbon Society (2010- present).

5.       On Scientific Committee of Pacific Basin Conference on Adsorption Science and Technology II, Australia, May 2000.

6.       On the Scientific Committee of IV International Symposium on Surface Heterogeneity in Adsorption and Catalysis, August 2006

7.       On the Scientific Committee of 2nd Carbon for Environmental Protection Conference, October 2009.

8.       On the Advisory Board of 1st United Arab Emirates Conference on Pure and Applied Chemistry (ECPAC11)-American University of Sharjah, February 2011.

9.       On the Scientific Committee of Colloids and Materials, Amsterdam 2011.

10.    On the Advisory Committee of International Carbon Conference, Krakow, Poland 2012

11.     Session Organizer /Chair at Annual ACS Meetings in Philadelphia (2004) and San Diego (2005).

12.    Editor “Activated Carbon Surfaces in Environmental Remediation”, Elsevier, 2006.

13.    Visiting Professor, Department of Chemical Engineering, The University of Queensland, Australia; Fall 2006

14.    Guest Professor/ Sky Scholar, Dalian University of Technology, China 2006-2009.

15.    Visiting Professor, University of Orleans, France, Fall 2009.

16.    Plenary Lecturer at Brazilian Institute of Chemical Engineers Meeting, Iguassu Falls, Brazil, September 2010.

17.    Plenary Lecturer of Carbon in Catalysis, CarboCat4, Conference, Dalian, China, November 2010.

18.    Invited speaker to 1st International Symposium on Chemistry of Energy Conversion and Storage (Germany; February 2001).

19.    Invited Keynote speaker to  Carbon for Energy storage and Environment Protection  IV (France, September 20011)

20.   Discussion leader at Hydrocarbon Resources Gordon Conference (January 2009)

21.    Excellence in Review Award; Environmental Science and Technology, 2005

22. Excellence in Review Award; Carbon, 2008

Featured in New York Times:  "Secret Weapon Against Sludge: Sludge" by Antoni DePalama; February 21, 2005.

 

 

CURRENT RESEARCH INTERESTS

Environmental Application of Adsorption

Modification of materials

New sorbents and catalysts

Surface characterization

Methane/natural gas/hydrogen storage

Adsorption/desorption phenomena

Gas separation

Deep desulfurization of fuels

Catalytic photooxidation

Graphite oxide based composite adsorbents

 Graphene/MOF composites as adsorbents

Gas sensors

Carbon materials based supercapacitors for energy storage

 

DESCRIPTION OF RESEARCH 

Study of Granular Activated Carbons as Adsorbents of Hydrogen Sulfide

We are working on monitoring the performance of activated carbons used to remove hydrogen sulfide odor in the City of New York Water Pollution Control Plants. So far mainly caustic-impregnated carbons have been used for air deodorization. Such carbons are expensive, create a risk of self ignition and require special precaution. That is why we are carrying out laboratory experiments along with pilot and fill-scale tests to study the possibility of replacement of caustic carbons with unmodified ones. Since the surface of activated carbons is very complicated from the point of view of chemistry and porous structure we are trying to define factors which enhance the adsorption of hydrogen sulfide and its oxidation to water soluble species that may make the regeneration of exhausted carbons using water feasible.

Mechanism of Mercaptan Adsorption on Activated Carbons

The process of removal of hydrogen sulfide and mercaptans is of great scientific and practical importance. It is because many natural raw materials, including copper ores and energy sources (oil, gas, coal, geothermal vapor, etc.) contain considerable amounts of sulfur derivatives. Those derivatives are formed in biological or chemical reactions such as thermal or anaerobic decomposition of organic materials. Sulfur derivatives are also considered as strong pollutants emitted to the atmosphere from various industries such as petroleum, paper, viscose, and food industries. From those, the most desirable to remove are hydrogen sulfide and thiols (mercaptans). They are odorous gases with significant toxicity. Since scientific reports describing sorption of methyl mercaptan which have been published so far do not discuss the influence of the carbon surface on the removal/oxidation of thiols, major goals of the proposed research are: (a) to study the performance of various commercial activated carbons as adsorbents of methyl mercaptane; (b) to modify the surface of carbons toward increasing their performance as adsorbents of methyl mercaptan; (c) to derive the mechanism of adsorption of methyl mercaptan on activated carbons. Since many odoriferous compounds have sulfur in their chemical formulas, investigation of the mechanism of methyl mercaptan removal will shed some light on the process of removal of odoriferous species in general.

Activated Carbons as Adsorbents of Traces of Odoriferous Compounds

Major goals of the research are: (a) to study the performance of various commercial activated carbons as odor adsorbents; (b) to modify the surface of carbons toward increasing their performance as adsorbents of specific odor compounds; (c) to study the mechanisms of adsorption of representative volatile constituents of human odor on activated carbons. The following analytical methods are used to characterize the pore structure and surface chemistry: potentiometric titration (pKa distribution), Boehm titration, volumetric sorption experiments (gas and vapor) with modern DFT analysis, FTIR, DTA/TG analysis, thermometric titration, and inverse gas chromatography with MS detector. We expect our work to throw new light on a number of unanswered questions regarding the application of carbons as deodorants. This includes: (1) what is the mechanism by which adsorption/immobilization occurs ?; (2) how is the adsorption affected by type, density and placement of the active sites on the surface?; (3) is there an optimum density, type, and geometric arrangement of sites that give a maximum adsorption of odorous species? Based on the answers to those questions the mechanism of adsorption will be proposed.

Activated of Organic Pollutants from Aqueous Phase on Activated Carbons

The mechanisms of adsorption of polar molecules such as water, methanol or chlorophenol on activated carbons are still not fully understood. The description of these molecules behavior at low relative pressure is important since activated carbons are widely used in the chemical, oil, gas and pharmaceutical industries for separations and purification of process streams, and for treatment of waste streams. However, it was previously found that the adsorption of polar molecules is strongly influenced by surface chemistry of carbon, the experimental results presenting adsorption at very low pressure region where surface groups - adsorbate interaction are significant have not been abandoned in the literature. The aim of this project is to develop improved models of polar molecules adsorption on activated carbons at low relative pressure. Experimental measurements will be done on carbons having a variety of well described surface chemical groups (carboxylic, lactonic, phenolic, etc.) and relatively homogeneous pore structures. The surface of carbon will be characterized by the variety of analytical methods based on titration, thermal analysis and spectroscopy. The isotherms of polar molecules will be measured at various temperatures (p/po 0.001-0.3). From the isotherms the isosteric heats of adsorption will be calculated. Then their values and changes with surface coverage will be analyzed in conjunction with the detailed characteristics of the carbon surface. The work is expected to throw new light on understanding the mechanism of adsorption of polar molecules and how adsorption is influenced by the type, placement and density of various surface chemical groups

 

COMPOSITE ADSORBENTS BASED ON INDUSTRIAL/MUNICIPAL WASTES

Industrial sludges/wastes/ ashes  often contain  transition metals which can work as catalysts in many processes such as hydrogen sulfide oxidation or desulfurization of liquid fuel. Pyrolyzing those wastes  in  various proportions with carbonaceous "fillers" results in materials with high capacity for removal of sulfur from gas or liquid phase via reactive adsorption. This happens owing to high dispersion of catalysts  significant volume of pores.

As a result of the technology applied a new class of composite materials is obtained.

On those materials  following processes are tested:

Removal of hydrogen sulfide from air

Desulfurization of bio gas

Desulfurization of liquid  fuels

METAL CONTAINING CARBONS FOR REACTIVE ADSORPTION

Nanoporous carbon are obtained from metal containing polymers via carbonization  either  as a bulk materials or within  inorganic templates (silica, ordered silica, alumina, zeolites). By changing the kind of polymer , its functional groups and the kind of metals new catalyst are obtained and tested in various  reactions.

SORBENTS AND MECHANISMS OF REMOVAL

Various sorbents are tested as adsorbents of industrial toxic gases such as NH3, NOx, SO2, Ethylene oxides, etc. Depending on the properties of adsorbates and the mechanism of  surface reaction expected various surface modifications are targeted towards  surface retention of  toxic species.

GRAPHITE OXIDES BASED COMPOSITE ADSORBENTS

A new class of adsorbents for removal of toxic gases is prepared from graphite oxide using their interactions with inorganic catalytic phases.

NANOENGINEERED  ADSORBENTS

A major goal of this project is the synthesis of composites, which will combine the favorable attributes of activated carbons, graphite oxides, MOFs and transition metal based catalysts; in particular the graphene component will lead to strong adsorption, and the MOF or catalytic species of nanosize dimensions - to surface reactions enhancing removal of TICs.  Syntheses will be followed by characterization. We plan to study NOX (NO2/NO), AsH3 and PH3 interactions with the nanocomposites. MOF chosen for the study will include those water stable with potentially active Cu and Fe sites. For incorporation of nanocrystal species, silver, iron, copper, and their oxides will be used.

We plan to address the following questions related to reactive adsorption of small molecule gases on Graphene/ MOF, graphene/ nanocrystal composites and on nonospecies modified carbons: 1) Which synthesis route leads to the most porous and most reactive nanocomposites? 2) Can we control the position and type of active centers groups to design the porosity and the  exact location of the active centers?  3) Do the experimental conditions affect the molecular level interactions? 4) Can we design revolutionary optimal nanocomposites for air decontamination?  5) For such optimal materials, what is their performance in removal of TICs

Deep desulfurization of Liquid fuel

Recent environmental regulations set the limits of sulfur in gasoline to 30 ppm and in diesel fuel to 15 ppm  (2006). Even though in the off-road fuel 500 ppm of sulfur is still an acceptable level, the limits are set to be 15 ppm by 2010. Hydrodesulfurization (HDS) is a method, which is able to remove the majority of sulfur-containing compounds from fossil fuel. In spite of the high efficiency and established technological importance of HDS it is not able to remove completely dibenezothiophenes. Especially 4,6 – dimethyldibezothiophene is considered as resistant to any chemical reactions.

In the research program proposed here we seek to define the features of carbonaceous adsorbents that govern the deep desulfurization process and to develop efficient diesel fuel desulfurization media. The removal process we target is based on reactive adsorption of DBT and 4, 6-DMDBT from very low concentration of 20 ppm sulfur. In the “best case scenario”, thiophenic molecules will first be specifically adsorbed on the catalytic metal center/ heteroatom containing groups and then the breaking of the carbon sulfur bond will occur with retention of sulfur on the surface and a return of the hydrocarbon molecule to the fuel stream.  In the “worse case scenario”, the DBT and 4,6-DMDBT molecules will be specifically adsorbed in the pore system on metal oxides, sulfides, sulfur, nitrogen, phosphorus or oxygen containing centers. Various scenarios of the in-between interactions can exist.  We will provide the detailed experimental procedure for the preparation of the most efficient removal media (from the point of view of the capacity, selectivity and regeneration feasibility) along with the mechanism of the process. The performance of adsorbents in desulfurization from liquid phase will be linked to their surface features. This will open new routes for designing more efficient and cost effective adsorbents and catalysts.

Our review of the literature and research experience lead to the following research questions related to achieving our objectives and to the development of new technology: 1) Which temperature of carbonization does lead to the most effective adsorbent/catalyst? 2) Which heteroatoms do enhance the capacity and selectivity of adsorption? 3) Which metals/ surface groups or their combinations are the most effective desulfurization catalysts? 4) Which content of metal does result the highest capacity? 5) What are the products of surface reactions (if any)?  6) What is the mechanism of adsorption? 7) Can we efficiently regenerate the spent adsorbents? 8) Can we design an adsorbent (based on the commercial carbonaceous precursors) with the surface features leading to the effective deep desulfurization of diesel fuel?

Graphene Oxide /MnO2 Composites: Investigation of energy storage capability

 

MnO2 is an effective, low cost material for many different types of electrochemical devices, including primary alkaline cells, primary and secondary lithium cells, acidic supercapacitors and air cathodes.  MnO2, like most oxides, sufferers from poor electronic conductivity, ultimately limiting the power performance without appreciable amount of conductive binder.  In this study we examine the performance of the composited formed by addition of graphene phase to in situ  synthesized  MnO2 as super capacitors and air catalysts.  We hypothesize that this new form of alpha-MnO2 will have appreciably better power performance per unit volume because of 1) lowered effective series resistance and 2) improved catalytic activity in the case of the air electrode. 

 

RESEARCH GRANTS

National Research Council/ National Academy of Sciences;  Fall 1997
Travel grant to Ukraine to start collaboration with Ukrainian Academy of Sciences ---$ 2,000
NYC DEP ; Jan. 98-Jan. 99
Study of Granular Activated Carbons ---$272,319
PSC-CUNY; July 98- June 00
Effect of Surface Chemistry of Activated Carbons on Sorption of Polar Molecule---$7,910
NASA (PAIR); (associate investigator) June 98-June 01
Remote Sensing and Environmental/Climate Research
NYC DEP ; May 99-May 02
Study of Granular Activated Carbons--- $682,896
CUNY Collaborative Incentive Grants Program; Sept.99-Aug.01
Activated Carbons Obtained from New York City Municipal Sludge as Sorbents for Sulfur Dioxide (with Prof.David Locke, QC)--- $32,000
Graduate Research Technology Initiative: 1999
Evaluation of the levels of Contaminants and Pollutants in Water and Air in New York--- $50,000
Petroleum Research Foundation; Sept.00-Aug.02

        The Mechanism of Methyl Mercaptan Adsorption/Oxidation on Activated Carbons---             $60,000

DuPont; Feb. 01- Jan. 02


Determination of Surface pKa Distribution using Titration Methods in Polar and Non-Polar Solvents--- $15,000

NATO: April 2002-2004

        Removal of H2S and CH3SH on Nitrogen Containing Activated Carbons--$ 20,000

Synagro Corporation: Oct. 01- Sept. 02

TERRENE® Modified with Spent Oil As A Precursor for Efficient Adsorbents for H2S and SO2 Removal---$10,000
NYC DEP: May 02 - May 05

Study on Granular Activated Carbons --- $ 476,490
CRDF (USA - Moldavia): March 02 - April 04

Activated Carbons for Water Treatment --- $ 5,800
NYSERDA: Feb 04 - June 04

Sewage Sludge Enriched Adsorbents Removal of Acidic Gases  --- $ 41,000
NYC DEP: May 05- May 07

Study of Granular Activated Carbon ----$ 562,000

Army Research Office: Oct.05-Oct.09

Sorbents and Mechanism of Removal ---$ 370,000

NYSERDA: April 06-April 07

Desulfurization of Biogas on Industrial Sludge Derived Materials---$50,000

NSF         April 08-March 11

Removal of Toxic  Gases by Intercalation and Reactive Adsorption ----$177,927

 NYC DEP   May 08-May 10

Study of Granular Activated Carbons     ---- $670,000  

NSF   April 08-March 11

Removal of Toxic Gases by Intercalation and Reactive Adsorption  -----       $177,927

 NSF    Oct.09- Sept. 12

Investigation of Factors Affecting Adsorption Capacity and Selectivity of Activated Carbon in Highly Efficient Desulfurization of Diesel Fuel:                                                ----  $292,000

ARO   Feb.10-Jan. 13

Nanoengineered Carbon-Based Materials For Reactive Adsorption of Toxic Industrial Compounds                                                                                                         ------$370,000

 NYC DEP         May 10-May 10, 2013

Study of Granular Activated Carbons                               ------ $1,100,200

Micromeritics Instrument Corporation ( 2011)- ASAP 2050     ----$98,000

ARO –DURIP:  2011

Acquisition of High Sensitivity Instruments to Enhance the  Study of Reactive Adsorption on Nanoengineered Materials And Their Application In Filters And Gas Sensors           -------- $ 110,000

 

 

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last updated: August 10, 2011

updated by TJB