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JournalofElectroanalyticalChemistry897(2021)115557
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JournalofElectroanalyticalChemistry
journalhomepage:www.elsevi er.com/locate/jelechem
AnovelstrategytosynthesizePt/CNTsnanocatalystwithhighlyimproved activityformethanolelectrooxidation
PingpingYang a,1,ZihanZhou a,1,TaotaoZheng a,ChunmengGu a,XiGong a,YuanyuanZhang e,YixiXie b,⇑ , NianjunYang d,e,JunjieFei a,b,c,⇑
a KeyLaboratoryofEnvironmentallyFriendlyChemistryandApplicationsofMinistryofEducation,CollegeofChemistry,XiangtanUniversity,Xiangtan411105,People’sRepublicofChina
b KeyLaboratoryforGreenOrganicSynthesisandApplicationofHunanProvince,CollegeofChemistry,XiangtanUniversity,Xiangtan411105,People’sRepublicofChina
c HunanInstituteofAdvancedSensingandInformationTechnology,XiangtanUniversity,Xiangtan411105,People’sRepublicofChina
d InstituteofMaterialsEngineering,UniversityofSiegen,Siegen57076,Germany
e SchoolofChemistryandEnvironmentalEngineeringKeyLaboratoryforGreenChemicalProcessofMinistryofEducationHubeiKeyLabofNovelReactorandGreenChemical Technology,WuhanInstituteofTechnologyWuhan430073,People’sRepublicofChina
ARTICLEINFO
Keywords: Directmethanolfuelcells
Deepeutecticsolvents
Ptcatalyst
Multi-walledcarbonnanotubes
Methanoloxidation
ABSTRACT
MaximizingtheactivityofPtcatalystsformethanoloxidation(MOR)whileminimizingadsorbedCOpoisoning duringMORremainsamajorchallenge.WehavepreparedPtnanoparticlesonmulti-walledcarbonnanotubes (MWCNTs)-supportedcatalystsindeepeutecticsolvents(DES).Thesenanocatalystsareshowntobetemperaturedependentasthecatalystpreparedat80°C(referredtoPt/CNTs-80)showshighercatalyticperformance towardmethanol(peakcurrent:1028.6mAmgPt 1)andbetterCOanti-poisoningcapability(onsetpotential: 0.31V,peakpotential:0.61V)comparedwithPt/CNTs-25(synthesizedinDESat25°C)(520.7mAmgPt 1 , 0.56V,0.64V),Pt/CNTs-W(synthesizedinwaterat80°C)(260.8mAmgPt 1,0.58V,0.66V)andcommercial Pt/C(177.8mAmgPt 1,0.63V,0.71V).ThisstudyprovidesasuitablestrategyforthepreparationofhighperformancePt-basedelectrocatalystsforthedirectmethanolfuelcell(DMFC).
1.Introduction
Thedirectmethanolfuelcell(DMFC),agreen,sustainableenergy source,hasshownsomeadvantagesoverotherenvironmentally friendlyenergysources:asimplefabricationprocess,safeliquid methanol,higherenergydensity,lowoperatingtemperature,andenvironmentalfriendliness [1–5].Methanolundergoeselectrochemical oxidationtocarbondioxidethroughacarbonaceousintermediate (e.g.,CO)attheanodeofaDMFC.Methanoloxidation(MOR)iskineticallyslowanddoesrequireanelectrocatalyst(e.g.,Ptanditsalloys). However,thehighpriceandscarceresourcesofPtarecommercializationbarriersforthewidespreaduseofDMFCs.Moreover,Pt-basedcatalystsaresusceptibletocarbonaceousintermediates,suchasCO,that canbeadsorbedonthesurfaceofPtandleadtoserioustoxiceffects thatmayreducetheservicelifeofthecatalyst.Therefore,itisimperativetosynthesizehighperformanceelectrocatalysts(i.e.,thatcan maximizecatalyticcapacitywhileminimizingtheCOpoisoningeffect duringMORprocessing).
Tomeetthisdemand,somePtnanostructures(suchasnanoclusters [6],nanoflowers [7],hollownanospheres [8],nanonetworks [9], nanocubes [10],etc.)havebeensynthesizedbyvariousmethods. Thesespecialstructureshavemoreactivesitesandlargeractivesurfaceareas,andtheiractivitiesaregreatlyimprovedcomparedwith commercialPt/Ccatalysts.Ontheotherhand,thesynthesisof bimetalliccatalystshassolvedtheCOpoisoningproblemonPt-based catalysts,suchasPtM(whereM=Ru [11],Co [12],Cu [13,14],Bi [15],W [5],Fe [16],Rh [17],Pd [18].Theadditionofcheaptransitionmetalscanprovidemoreactivesitestoadsorbhydroxidesothat intermediatespeciescanbeeasilyremovedatlowpotential.ThelatticecompressionandchangesinelectronicstructureofPtcanalso weakentheadsorptionenergyofintermediates.
Asanalternativemethod,morestudieshavefocusedonhowto obtainPt-basedcatalystswithsmallerparticlesandbetterdispersion [19,20].Forexample,Fan’sgroupreportedanovelelectrocatalystconsistingofPtnanoparticlessupportedonapolyindole(PIn)-functionalized(MWCNTs)composite(Pt/PIn-MWCNTs)foruseintheMOR.The https://doi.org/10.1016/j.jelechem.2021.115557 Received23April2021;Receivedinrevisedform12July2021;Accepted20July2021 Availableonline24July2021 1572-6657/©2021PublishedbyElsevierB.V.
⇑ Correspondingauthorsat:KeyLaboratoryofEnvironmentallyFriendlyChemistryandApplicationsofMinistryofEducation,CollegeofChemistry,XiangtanUniversity,Xiangtan 411105,People’sRepublicofChina.
E-mailaddresses: xieyixige@xtu.edu.cn (Y.Xie), fei_junjie@xtu.edu.cn (J.Fei).
1 Theseauthorscontributedequallytothework.
Ptnanoparticleswereapproximately3.0nminsizeanduniformly depositedonthesurfaceofPIn-MWCNTswithmuchhigherelectrocatalyticactivity,durability,andCOtolerancethanPt/MWCNTsand commercialPt/Ccatalysts [21].Inaddition,Zhaoetal.constructed well-dispersedPtCualloynanoparticles(NPs)onthree-dimensional nitrogen-dopedgraphene(PtCu/3D N-G)electrocatalystbyaconventionalhydrothermalmethodcombinedwithahigh-efficiencymicrowave-assistedpolyolprocess.Theas-preparedPtCu/3D N-G electrocatalystpossesseslargerelectrochemicalactivesurfacearea, loweronsetpotential,highercurrentdensity,andbettertoleranceto COpoisoningthanPtCuNPsonreducedgrapheneoxideandXC-72 carbonblackinacidicsolution [22].Thesemethodsdidenhancethe activityofMOR,aswellastheresistancetoCOpoisoning.However, thesestrategiesarecomplexandrequirelargequantitiesoftoxic organicsolvents.Soitisimperativeto findasimple,environmentally friendlysynthesisstrategy.
Deepeutecticsolvents(DES)havecharacteristicsofawideelectrochemicalwindow,negligiblevaporpressure,goodelectricalconductivity,non-toxicity,andbiodegradability [23,24].Hammonsetal. electrodepositedPdnanoparticlesinDESandrevealedtheinteractions betweentheparticlesandsolvent [25].TheysuggestedthatthisenvironmentallyfriendlymediumcanbeusedtostabilizePdnanoparticles insitu.IntheabsenceofDES,theparticlesbecomeunstable.This resultshowsthatDESplaysanimportantroleinstabilizingnanoparticlesandcanbeusedtoprepareexcellentactivecatalysts.
Nowadays,carbonmaterials,suchascarbonblacks [26],carbon nanofibers [27],orderedmesoporouscarbon [28],carbonnanotubes [29–31],graphene [32],porousgraphene [33] etal.,arebeingused inmoreandbroaderapplications.Inparticular,MWCNTsshowa uniquemorphologyandexcellentproperties,includinghighspecific surfacearea,corrosionresistance,goodelectricalconductivity,and highstability [13,34,35]
Herein,Pt/CNTs-80waspreparedbyanenvironmentallyfriendly one-stepchemicalreduction(Scheme1).BasedonthelargeESCA, thePt/CNTs-80exhibitexcellentMORelectrocatalyticactivity,longtermdurability,andCO-toleranceabilitycomparedtoPt/CNTs-25, Pt/CNTs-W,andPt/C.
2.Experimental
2.1.PreparationofPt/CNTs-80
DESwaspreparedwithcholinechloride/urea [13].Functionalized MWCNTswereobtainedbytheacidificationofMWCNTs(referredto CNTs-AO) [36–38].First,20mgCNTS-AOwascompletelydispersed in20mLDESwithultrasonicmixing.ThenappropriateamountsofH2PtCI6 6H2O/DESssolutionandNaBH4 (molarratioofNaBH4/H2PtCl6 =10)wereaddedwithstirringfor3hat80°CandpH=9. Thecatalystswerecentrifugedanddriedovernightat60°C.Inaddition,Pt/CNTs-25,Pt/CNTs-40,Pt/CNTs-60,andPt/CNTs-100were preparedbythesamemethodexceptthatthereactiontemperatures were25°C,40°C,60°C,and100°C.Besides,thePt/CNTs-Wcatalyst wassynthesizedinwaterat80°Cbythesamemethod.CommercialPt/ CwaspurchasedfromtheXianfengNanomaterialsTechnologyCo. LTD,Nanjing.
2.2.Physicalcharacterization
X-raydiffraction(XRD)wasperformedonaRigakuD/MAX2500 v/pc(Japan)diffractometertoanalyzethecatalyststructure.Thermo FisherK-AlphawasusedforX-rayphotoelectronspectroscopy(XPS) measurements.High-resolutiontransmissionelectronmicroscopy (HRTEM,JEOLJEM-2100F)wasusedtoanalyzethemorphologyof thesamples.Aninductivelycoupledplasma-opticalemissionspectrophotometer(ICP-OES,Agilent720)wasusedtoanalyzethePtcon-
tentanalysisofPt/C,Pt/CNTs-W,Pt/CNTs-25,andPt/CNTs-80 catalysts,whichweredeterminedtobe20%,18.6%,19.5%,and 19.6%,respectively.Inaddition,themassesofPtinPt/C,Pt/CNTsW,Pt/CNTs-25,andPt/CNTs-80catalystswere3.68,3.51,3.72,and 3.81 μg,respectively.ThePtloadingsontheworkingelectrodesof thesethreecatalystswere14.7,14.0,14.9,and15.2 μgcm 2
2.3.Electrochemicalmeasurements
Atraditionalthree-electrodesystemonaCHI660Delectrochemical workstationwasusedtotestallelectrochemicalbehaviorofthecatalysts.Platinumfoilandasaturatedcalomelelectrode(SCE)were employedforthecounterelectrodeandreferenceelectrode,respectively.Twomgcatalystwasdispersedina1mLsolutionof950 µL redistilledwaterand50 μLNafionsolution(0.5wt%).A10 μLsuspensionwasdrippedontheGCelectrodeatroomtemperaturebeforeelectrochemicaltesting.
TheMORofallcatalystswascarriedoutin0.5MCH3OH+0.5M H2SO4 solution(SCE).TheoperationofCOstrippingvoltammetryisas follows: first,N2 waspassedthrough0.5MH2SO4 solutionfor15min toremoveoxygenfromthesolution.Then,COwaspassedthroughthe solutionfor15mintoachievesaturatedCOabsorptionwhilemaintainingavoltagesweepof 0.2and0.0V.Thesolutionwasthen passedthroughwithN2 for25mintocompletelyremovethedissolved COwhileavoidinginterferencewithoxygenintheair.Allcurrentin theelectrochemicalexperimentisexpressedasnormalizedcurrent permgofthePtloadontheGCE [39,40].
3.Resultsanddiscussion
3.1.XRDanalysis
TheXRDpatternsofPt/CNTs-25(a)andPt/CNTs-80(b)catalysts areshownin Fig.1A.ThetwocatalystsshowdiffractionpeaksofPt (111),Pt(200),Pt(220),Pt(311),andPt(222)locatedat 2θ =39.8°,46.3°,67.7°,81.5°,and85.8°,respectively [13].Moreover, thediffractionpeaksofPt(220)andPt(311)ofPt/CNTs-80display broaderdiffractionpeakscomparedwiththePt/CNTs-25catalyst,suggestingsmallersizesofPtnanoparticlesinPt/CNTs-80 [13].TheaveragecrystallitesizesofPt/CNTs-80andPt/CNTs-25weredetermined tobe4.1nmand6.3nm,ascalculatedfromthePt(220)diffraction peakusingScherrer'sequation [19].TheEDSspectrumofPt/CNTs80showsthatPtwassuccessfullyloadedontotheMWCNTs(Fig.1B).
3.2.TEMandXPScharacterization
TheTEMimagesandcorrespondingsizedistributionhistogramsof Pt/CNTs-80(A,B,C,D)andPt/CNTs-25(E,F)areshownin Fig.2.As shownin Fig.2AandB,mostofthePtnanoparticlesareuniformlydispersedontheMWCNTswithoutforminglargeclusters. Fig.2Cshows thatthecorrespondingsizedistributionhistogramofthePt/CNTs-80 catalystisabout4.2nm,whichisclosetotheXRDdata.Alatticespacingvalueof0.236nmisconsistentwiththatofthePt(111)planes (Fig.2D) [41].Incontrast,PtnanoparticlesofthePt/CNTs-25 (Fig.2E)andPt/CNTs-Warecharacterizedbypoordistributionand alargenumberofaggregates.TheaverageparticlesizesofPtinPt/ CNTs-25(Fig.2F)andPt/CNTs-W(Fig.S1)catalystsareabout6.2 and11.6nm,whicharenearly1.5and2.8timesthatforthePt/ CNTs-80catalyst.ThisphenomenonsuggeststhatDESfavorstheformationofsmallerparticles.Moreover,asuitablereactiontemperature isanotherreasonfortheformationofsmallerparticlesinDES,ahigh viscositysolvent [42].Underthereactionconditionof25°C,theviscosityofDESisstillhigh,whichisnotconducivetothetransmission ofreactionmaterials,thusleadingtothefailureoftimelydispersion andagglomerationofnanoparticlesobtainedbyreduction.Thehigher
Scheme1. SchematicillustrationofthestrategyforthesynthesisofPt/CNTs-80catalyst.
Fig.1. (A)XRDpatternsofPt/CNTs-25(a)andPt/CNTs-80(b)catalysts;(B)EDSspectrumofPt/CNTs-80.
Fig.2. TEMimagesandcorrespondingsizedistributionhistogramsofPt/CNTs-80(A,B,C,D)andPt/CNTs-25(E,F)catalysts.
reactiontemperatureof80°Ccanincreasethereactionrateandmass transfer,resultinginsmalleranduniformlydispersednanoparticles [13].
ThesurfacecompositionandchemicaloxidationstateofthecatalystwerefurtherexploredbyXPS. Fig.3AshowstheXPSsurveyspectraofPt/CNTs-80.SignalscorrespondingtoC1s,O1s,Pt4f,Pt4d, andPt4pwereobserved,whichshowedthatthePt/CNTs-80catalyst wassuccessfullyprepared [43].ThehighresolutionspectrumofPt/ CNTs-80in Fig.3BshowsthatthedeconvolutionofthehighlyasymmetricC1sphotoemissionyieldstwopeaksat284.8and286.4eV duetotheC CandC ObondsofMWCNTs,exhibitingthatfunctionalizedMWCNTsweresuccessfullyprepared.ThePt(4f)spectrumof Pt/CNTs-80isshownin Fig.3C,wheredifferentpeaksindicatethe existenceofdifferentPtoxidationstates.Thebindingenergiesof 71.3eV(Pt4f7/2)and75.5eV(Pt4f5/2)originatefrommetallic Pt(0) [44],andthepeakslocatedat72.1eV(Pt4f7/2)and 74.6eV(Pt4f5/2)belongtothePt(+2)state [21,45].Basedon therelativeareasofthesepeaks,thepercentagesofPt(0)andPt (+2)speciesarecalculatedtobe66.7%and33.3%,respectively,indicatingthattheDESfavorshigheramountsofmetallicPt.
3.3.Electrochemicalcharacterization
Fig.4 showsthatthepreparationconditions,pHvalues(A), amountofsodiumborohydride(B),reactiontime(C)andreaction temperature(D)wereoptimizedduringthepreparationprocessof thecatalysts.Somereportsindicatedthatparticlesizeandstructure wereinfluencedbythepHofthesolution [46,47].Besides,theamount ofsodiumborohydridewillsignificantlyaffectthedispersionofPt nanoparticles,whereamolarratioofNaBH4/H2PtCl6 =10wasfound tobeappropriate [19,47].Themassactivity(MA)ofthecatalystspreparedbytheshortestorlongestreactingtimewasfoundtobelower basedoneitherlowPtloadingamountsorpoorPtnormalizedECSA fromthelargeparticlesize.Inaddition,areactiontimeof3hseems tobethebestforthepreparationofcatalyst [48].Finally,theelectron
transferabilityofthecatalystalsoimprovedwithappropriatereaction temperature [26].Asshownin Fig.4,pH=9,molarratioofNaBH4/ H2PtCl6 =10,3h,and80°Cweredeterminedtobeoptimalconditions,whichwillbelaterappliedinthepreparationprocess.
Fig.5 showsthecyclicvoltammogramsofthePt/CNTs-80(a),Pt/ CNTs-25(b),Pt/CNTs-W(c),andPt/C(d)catalystsin0.5MH2SO4 solution(50mVs 1).Thehydrogenadsorption/desorptionregions between 0.2and0.1VandPtoxidation/reductionpeaksshowtypicalCVcurvesofPt [49].Theelectrochemicalactivesurfaceareas (ECSA)ofthecatalystswerecalculatedbymeasuringthehydrogen adsorption/desorptionchargesafteradouble-layercorrectionand assumingavalueof210 μCcm 2 fortheadsorptionofahydrogen monolayeraccordingtoEq (1):
ECSA ¼ QH = QHmono WPt ðÞð1Þ
Aftersubtractingthechargefromthedouble-layerregion,theintegratedchargewithinthehydrogenadsorptionareaintheCVcurvesis QH (mC).TheQHmonoisthecharge(210 µCcm 2)correspondingto hydrogenmonolayeradsorptiononthePtsurfaceandWPt isthemass ofPt [50].Ultimately,theECSAofthePt/CNTs-80(a),Pt/CNTs-25 (b),Pt/CNTs-W(c),andPt/C(d)werecalculatedtobe56.20,36.2, 27.6,and21.3m2 g 1,respectively.Thesmallerparticlesprovideda largerECSAvalueforPt/CNTs-80.
Fig.6AshowstheCVcurvesofthePt/CNTs-80(a),Pt/CNTs-25(b), Pt/CNTs-W(c)andPt/C(d)catalystsin0.5MCH3OH+0.5MH2SO4 solution.Whenmethanolwaselectrocatalyzedbythecatalysts,two irreversiblecurrentpeaksappeared [51,52].Theforwardscanat approximately0.65VisduetotheanodicpeaktowardMOR.Another anodicpeakatapproximately0.49Vinthereversescanisattributed totheoxidationofintermediatecarbonaceousspeciesformedduring theforwardscan [41,53].ForthePt/CNTs-80catalyst(a),thepeak currentdensityintheforwardscanwas1028.6mAmgPt 1,whichis higherthanPt/CNTs-25(b,547.7mAmgPt 1),Pt/CNTs-W(c, 260.8mAmgPt 1),andPt/C(d,177.8mAmgPt 1)catalysts.Moreover, theonsetpotentialofMORforthePt/CNTs-80is0.32V,whichis
Fig.3. (A)XPSsurveyspectra;(B)C1sand(C)Pt4fspectrumofPt/CNTs-80catalyst.
Fig.4. CyclicvoltammogramsofcatalystswerepreparedatdifferentpHvalues(A),theamountofsodiumborohydride(B),reactiontime(C),andreaction temperature(D)in0.5MCH3OH+0.5MH2SO4 solution(50mV s 1).
Fig.5. CyclicvoltammogramsofPt/CNTs-80(a),Pt/CNTs-25(b),Pt/CNTs-W (c),andPt/C(d)in0.5MH2SO4 solution(50mVs 1).
lowerthanPt/CNTs-25(0.40V),Pt/CNTs-W(0.42V),andPt/C (0.45V),andshowsthatthecatalyticreactionoccursmoreeasily. Asshownin Fig.S2,thespecificcurrentdensity(1.83mAcm 2)of Pt/CNTs-80isalsohigherthanPt/CNTs-25(1.51mAcm 2),Pt/ CNTs-W(0.93mAcm 2),andPt/C(0.77mAcm 2)catalysts,further indicatingthatthepreparedPt/CNTs-80hasthebestintrinsicactivity fortheMOR.Inaddition,chronoamperometricmeasurementswere performedin0.5MCH3OH+0.5MH2SO4 solution(0.5V,3600s) tofurtherevaluatethelong-termelectrochemicaldurabilityofPt/ CNTs-80(a),Pt/CNTs-25(b),Pt/CNTs-W(c),andPt/C(d)catalysts towardMOR. Fig.6Bshowsthefourrapidcurrentdecaycurvesin theinitialstageindicatingthatelectrocatalystpoisoningoccurred duetotheformationofintermediatespecies,suchasCOads,CH3OHads, andCHOads [54].After3600s,thePt/CNTs-80stillretainedthehighestcatalyticactivity(159.8mAmgPt 1)whencomparedwiththePt/ CNTs-25(97.9mAmgPt 1),Pt/CNTs-W(35.8mAmgPt 1)andPt/C (3.85mAmgPt 1)catalysts.AfterCAtesting,thesizesofPtnanoparticlesinPt/CNTs-80arestillmuchsmaller(4.2nm)thanthatinPt/ CNTs-25(8.2nm)in Fig.S2.TheseresultsshowthatthePt/CNTs-80 catalystexhibitshigherelectrocatalyticactivityandstabilityfor
Fig.6. Cyclicvoltammograms(A)andcurrent-timecurves(B)ofPt/CNTs-80(a),Pt/CNTs-25(b),Pt/CNTs-W(c),andPt/C(d)in0.5MCH3OH+0.5MH2SO4 solution(50mVs 1).
Fig.7. COstrippingvoltammogramsofPt/CNTs-80(A),Pt/CNTs-25(B),Pt/ CNTs-W(C),andPt/C(D)catalystsin0.5MH2SO4 solution(50mVs 1).
MOR.Overall,thePt/CNTs-80catalystpresentsthebestMORmass activityincomparisonwithrecentresearchworksbasedonPt-based catalysts,asshownin TableS1
TheCOstrippingvoltammogramsandsubsequentCVcurvesforPt/ CNTs-80(A),Pt/CNTs-25(B),Pt/CNTs-W(C),andPt/C(D)catalysts in0.5MH2SO4 solutionareshownin Fig.7.Apparently,thehydrogen adsorption/desorptionabilitiesofallcatalystswerecompletelyinhibitedatthelowpotentialregion,whichisduetotheCOads speciesatthe activesites.Subsequently,thehydrogenadsorption/desorptionpeak reappearedwhentheadsorbedtoxicsubstancewasoxidized.Specifically,Pt/CNTs-80catalystshowsamorenegativepotential(onset potential:0.31V,peakpotential:0.61V)oftheadsorbedCOoxidation (Fig.7A)comparedwiththe(Fig.7B)Pt/CNTs-25(0.56V,0.64V),Pt/ CNTs-W(0.58V,0.66V),and(Fig.7C)Pt/C(0.63V,0.71V)catalysts, whichindicatesthatPt/CNTs-80showbettertoxicityresistance [15,55,56].
4.Conclusions
WeintroducedanovelmethodforthefabricationofPt/CNTs-80in DES.XRD,EDX,TEM,HAADF-STEM,XPS,ICP-OES,andelectrochemicalmeasurementswereusedtocharacterizethecatalyst,Pt/CNTs-80 exhibitedthebestMORelectrocatalyticactivity,long-termdurability, andCOtoleranceability,whencomparedwithPt/CNTs-25,Pt/CNTsW,andPt/C.Also,theresultsshowthatahighperformancenanocatalystpreparedinDESistemperaturedependent,andDES,asacatalyst preparationmedia,isquitepromising.
CRediTauthorshipcontributionstatement
PingpingYang: Writing-originaldraft. ZihanZhou: Datacuration. TaotaoZheng: Datacuration. ChunmengGu: Writing-review &editing. XiGong: Writing-review&editing. YuanyuanZhang: Writing-review&editing. YixiXie: Conceptualization,Methodology. NianjunYang: Conceptualization,Methodology. JunjieFei: Supervision.
DeclarationofCompetingInterest
Theauthorsdeclarethattheyhavenoknowncompeting financial interestsorpersonalrelationshipsthatcouldhaveappearedtoinfluencetheworkreportedinthispaper.
Acknowledgments
Thisresearchwas financiallysupportedbytheNationalNatural ScienceFoundationofChina(GrantsNos.21874114,21475114, 21775133,and31701613),theProjectofInnovationTeamoftheMinistryofEducation(IRT_17R90),theProjectofScienceandTechnology PlanofHunanProvince(2017XK2055),HunanProvincialInnovation FoundationforPostgraduate(CX20190484).
AppendixA.Supplementarydata
Supplementarydatatothisarticlecanbefoundonlineat https://doi.org/10.1016/j.jelechem.2021.115557.
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CHAPTER IX.
“Thou can’st not call that madness of which thou art proved to know nothing.”
—T : Apology
“This is not a matter of to-day, Or yesterday, but hath been from all times; And none hath told us whence it came or how!” S .
“Belief in the supernatural is a fact natural, primitive, universal, and constant in the life and history of the human race. Unbelief in the supernatural begets materialism; materialism, sensuality; sensuality, social convulsions, amid whose storms man again learns to believe and pray.” G .
“If any one think these things incredible, let him keep his opinions to himself, and not contradict those who, by such events, are incited to the study of virtue.”— J .
F the Platonic and Pythagorean views of matter and force, we will now turn to the kabalistic philosophy of the origin of man, and compare it with the theory of natural selection enunciated by Darwin and Wallace. It may be that we shall find as much reason to credit the ancients with originality in this direction as in that which we have been considering. To our mind, no stronger proof of the theory of cyclical progression need be required than the comparative enlightenment of former ages and that of the Patristic Church, as regards the form of the earth, and the movements of the planetary system. Even were other evidence wanting, the ignorance of Augustine and Lactantius, misleading the whole of Christendom upon these questions until the period of Galileo, would mark the eclipses through which human knowledge passes from age to age.
The “coats of skin,” mentioned in the third chapter of Genesis as given to Adam and Eve, are explained by certain ancient philosophers to mean the fleshy bodies with which, in the progress of the cycles, the progenitors of the race became clothed. They
maintained that the godlike physical form became grosser and grosser, until the bottom of what may be termed the last spiritual cycle was reached, and mankind entered upon the ascending arc of the first human cycle. Then began an uninterrupted series of cycles or yogas; the precise number of years of which each of them consisted remaining an inviolable mystery within the precincts of the sanctuaries and disclosed only to the initiates. As soon as humanity entered upon a new one, the stone age, with which the preceding cycle had closed, began to gradually merge into the following and next higher age. With each successive age, or epoch, men grew more refined, until the acme of perfection possible in that particular cycle had been reached. Then the receding wave of time carried back with it the vestiges of human, social, and intellectual progress. Cycle succeeded cycle, by imperceptible transitions; highly-civilized flourishing nations, waxed in power, attained the climax of development, waned, and became extinct; and mankind, when the end of the lower cyclic arc was reached, was replunged into barbarism as at the start. Kingdoms have crumbled and nation succeeded nation from the beginning until our day, the races alternately mounting to the highest and descending to the lowest points of development. Draper observes that there is no reason to suppose that any one cycle applied to the whole human race. On the contrary, while man in one portion of the planet was in a condition of retrogression, in another he might be progressing in enlightenment and civilization.
How analogous this theory is to the law of planetary motion, which causes the individual orbs to rotate on their axes; the several systems to move around their respective suns; and the whole stellar host to follow a common path around a common centre! Life and death, light and darkness, day and night on the planet, as it turns about its axis and traverses the zodiacal circle representing the lesser and the greater cycles.[484] Remember the Hermetic axiom: —“As above, so below; as in heaven, so on earth.”
Mr. Alfred R. Wallace argues with sound logic, that the development of man has been more marked in his mental organization than in his external form. Man, he conceives to differ
from the animal, by being able to undergo great changes of conditions and of his entire environment, without very marked alterations in bodily form and structure. The changes of climate he meets with a corresponding alteration in his clothing, shelter, weapons, and implements of husbandry. His body may become less hairy, more erect, and of a different color and proportions; “the head and face is immediately connected with the organ of the mind, and as being the medium, expressing the most refined motions of his nature,” alone change with the development of his intellect. There was a time when “he had not yet acquired that wonderfullydeveloped brain, the organ of the mind, which now, even in his lowest examples, raises him far above the highest brutes, at a period when he had the form, but hardly the nature of man, when he neither possessed human speech nor sympathetic and moral feelings.” Further, Mr. Wallace says that “Man may have been—indeed, I believe must have been, once a homogeneous race ... in man, the hairy covering of the body has almost entirely disappeared.“ Of the cave men of Les Eyzies, Mr. Wallace remarks further ” ... the great breadth of the face, the enormous development of the ascending ramus of the lower jaw ... indicate enormous muscular power and the habits of a savage and brutal race.”
Such are the glimpses which anthropology affords us of men, either arrived at the bottom of a cycle or starting in a new one. Let us see how far they are corroborated by clairvoyant psychometry. Professor Denton submitted a fragment of fossilized bone to his wife’s examination, without giving Mrs. Denton any hint as to what the article was. It immediately called up to her pictures of people and scenes which he thinks belonged to the stone age. She saw men closely resembling monkeys, with a body very hairy, and “as if the natural hair answered the purpose of clothing.” “I question whether he can stand perfectly upright; his hip-joints appear to be so formed, he cannot,” she added. “Occasionally I see part of the body of one of those beings that looks comparatively smooth. I can see the skin, which is lighter colored ... I do not know whether he belongs to the same period.... At a distance the face seems flat; the lower part of it is heavy; they have what I suppose would be called prognathous
jaws. The frontal region of the head is low, and the lower portion of it is very prominent, forming a round ridge across the forehead, immediately above the eyebrows.... Now I see a face that looks like that of a human being, though there is a monkey-like appearance about it. All these seem of that kind, having long arms and hairy bodies.”[485]
Whether or not the men of science are willing to concede the correctness of the Hermetic theory of the physical evolution of man from higher and more spiritual natures, they themselves show us how the race has progressed from the lowest observed point to its present development. And, as all nature seems to be made up of analogies, is it unreasonable to affirm that the same progressive development of individual forms has prevailed among the inhabitants of the unseen universe? If such marvellous effects have been caused by evolution upon our little insignificant planet, producing reasoning and intuitive men from some higher type of the ape family, why suppose that the boundless realms of space are inhabited only by disembodied angelic forms? Why not give place in that vast domain to the spiritual duplicates of these hairy, long-armed and half-reasoning ancestors, their predecessors, and all their successors, down to our time? Of course, the spiritual parts of such primeval members of the human family would be as uncouth and undeveloped as were their physical bodies. While they made no attempt to calculate the duration of the “grand cycle,” the Hermetic philosophers yet maintained that, according to the cyclic law, the living human race must inevitably and collectively return one day to that point of departure, where man was first clothed with “coats of skin;” or, to express it more clearly, the human race must, in accordance with the law of evolution, be finally physically spiritualized. Unless Messrs. Darwin and Huxley are prepared to prove that the man of our century has attained, as a physical and moral animal, the acme of perfection, and evolution, having reached its apex, must stop all further progress with the modern genus, Homo, we do not see how they can possibly confute such a logical deduction.
In his lecture on The Action of Natural Selection on Man, Mr Alfred R. Wallace concludes his demonstrations as to the development of human races under that law of selection by saying that, if his conclusions are just, “it must inevitably follow that the higher—the more intellectual and moral—must displace the lower and more degraded races; and the power of ‘natural selection,’ still acting on his mental organization, must ever lead to the more perfect adaptation of man’s higher faculties to the condition of surrounding nature, and to the exigencies of the social state. While his external form will probably ever remain unchanged, except in the development of that perfect beauty ... refined and ennobled by the highest intellectual faculties and sympathetic emotions, his mental constitution may continue to advance and improve, till the world is again inhabited by a single, nearly homogeneous race, no individual of which will be inferior to the noblest specimens of existing humanity.” Sober, scientific methods and cautiousness in hypothetical possibilities have evidently their share in this expression of the opinions of the great anthropologist. Still, what he says above clashes in no way with our kabalistic assertions. Allow to everprogressing nature, to the great law of the “survival of the fittest,” one step beyond Mr. Wallace’s deductions, and we have in future the possibility—nay, the assurance of a race, which, like the Vril-ya of Bulwer-Lytton’s Coming Race, will be but one remove from the primitive “Sons of God.”
It will be observed that this philosophy of cycles, which was allegorized by the Egyptian Hierophants in the “circle of necessity,” explains at the same time the allegory of the “Fall of man.” According to the Arabian descriptions, each of the seven chambers of the Pyramids—those grandest of all cosmic symbols—was known by the name of a planet. The peculiar architecture of the Pyramids shows in itself the drift of the metaphysical thought of their builders. The apex is lost in the clear blue sky of the land of the Pharaohs, and typifies the primordial point lost in the unseen universe from whence started the first race of the spiritual prototypes of man. Each mummy, from the moment that it was embalmed, lost its physical individuality in one sense; it symbolized the human race. Placed in such a way as
was best calculated to aid the exit of the “soul,” the latter had to pass through the seven planetary chambers before it made its exit through the symbolical apex. Each chamber typified, at the same time, one of the seven spheres, and one of the seven higher types of physicospiritual humanity alleged to be above our own. Every 3,000 years, the soul, representative of its race, had to return to its primal point of departure before it underwent another evolution into a more perfected spiritual and physical transformation. We must go deep indeed into the abstruse metaphysics of Oriental mysticism before we can realize fully the infinitude of the subjects that were embraced at one sweep by the majestic thought of its exponents.
Starting as a pure and perfect spiritual being, the Adam of the second chapter of Genesis, not satisfied with the position allotted to him by the Demiurgus (who is the eldest first-begotten, the AdamKadmon), Adam the second, the “man of dust,” strives in his pride to become Creator in his turn. Evolved out of the androgynous Kadmon, this Adam is himself an androgyn; for, according to the oldest beliefs presented allegorically in Plato’s Timæus, the prototypes of our races were all enclosed in the microcosmic tree which grew and developed within and under the great mundane or macrocosmic tree. Divine spirit being considered a unity, however numerous the rays of the great spiritual sun, man has still had his origin like all other forms, whether organic or otherwise, in this one Fount of Eternal Light. Were we even to reject the hypothesis of an androgynous man, in connection with physical evolution, the significance of the allegory in its spiritual sense, would remain unimpaired. So long as the first god-man, symbolizing the two first principles of creation, the dual male and female element, had no thought of good and evil he could not hypostasize “woman,” for she was in him as he was in her. It was only when, as a result of the evil hints of the serpent, matter, the latter condensed itself and cooled on the spiritual man in its contact with the elements, that the fruits of the man-tree—who is himself that tree of knowledge—appeared to his view. From this moment the androgynal union ceased, man evolved out of himself the woman as a separate entity. They have broken the thread between pure spirit and pure matter. Henceforth they will
create no more spiritually, and by the sole power of their will; man has become a physical creator, and the kingdom of spirit can be won only by a long imprisonment in matter. The meaning of Gogard, the Hellenic tree of life, the sacred oak among whose luxuriant branches a serpent dwells, and cannot be dislodged,[486] thus becomes apparent. Creeping out from the primordial ilus, the mundane snake grows more material and waxes in strength and power with every new evolution.
The Adam Primus, or Kadmon, the Logos of the Jewish mystics, is the same as the Grecian Prometheus, who seeks to rival with the divine wisdom; he is also the Pimander of Hermes, or the P D , in its most spiritual aspect, for he was less hypostasized by the Egyptians than the two former. These all create men, but fail in their final object. Desiring to endow man with an immortal spirit, in order that by linking the trinity in one, he might gradually return to his primal spiritual state without losing his individuality, Prometheus fails in his attempt to steal the divine fire, and is sentenced to expiate his crime on Mount Kazbeck. Prometheus is also the Logos of the ancient Greeks, as well as Herakles. In the Codex Nazaræus[487] we see Bahak-Zivo deserting the heaven of his father, confessing that though he is the father of the genii, he is unable to “construct creatures,” for he is equally unacquainted with Orcus as with “the consuming fire which is wanting in light.” And Fetahil, one of the “powers,” sits in the “mud” (matter) and wonders why the living fire is so changed.
All of these Logoi strove to endow man with the immortal spirit, failed, and nearly all are represented as being punished for the attempt by severe sentences. Those of the early Christian Fathers who like Origen and Clemens Alexandrinus, were well versed in Pagan symbology, having begun their careers as philosophers, felt very much embarrassed. They could not deny the anticipation of their doctrines in the oldest myths. The latest Logos, according to their teachings, had also appeared in order to show mankind the way to immortality; and in his desire to endow the world with eternal life through the Pentecostal fire, had lost his life agreeably to the
traditional programme. Thus was originated the very awkward explanation of which our modern clergy freely avail themselves, that all these mythic types show the prophetic spirit which, through the Lord’s mercy, was afforded even to the heathen idolaters! The Pagans, they assert, had presented in their imagery the great drama of Calvary—hence the resemblance. On the other hand, the philosophers maintained, with unassailable logic, that the pious fathers had simply helped themselves to a ready-made groundwork, either finding it easier than to exert their own imagination, or because of the greater number of ignorant proselytes who were attracted to the new doctrine by such an extraordinary resemblance with their mythologies, at least as far as the outward form of the most fundamental doctrines goes.
The allegory of the Fall of man and the fire of Prometheus is also another version of the myth of the rebellion of the proud Lucifer, hurled down to the bottomless pit—Orcus. In the religion of the Brahmans, Moisasure, the Hindu Lucifer, becomes envious of the Creator’s resplendent light, and at the head of a legion of inferior spirits rebels against Brahma, and declares war against him. Like Hercules, the faithful Titan, who helps Jupiter and restores to him his throne, Siva, the third person of the Hindu trinity, hurls them all from the celestial abode in Honderah, the region of eternal darkness. But here the fallen angels are made to repent of their evil deed, and in the Hindu doctrine they are all afforded the opportunity to progress. In the Greek fiction, Hercules, the Sun-god, descends to Hades to deliver the victims from their tortures; and the Christian Church also makes her incarnate god descend to the dreary Plutonic regions and overcome the rebellious ex-archangel. In their turn the kabalists explain the allegory in a semi-scientific way. Adam the second, or the first-created race which Plato calls gods, and the Bible the Elohim, was not triple in his nature like the earthly man: i.e., he was not composed of soul, spirit, and body, but was a compound of sublimated astral elements into which the “Father” had breathed an immortal, divine spirit. The latter, by reason of its godlike essence, was ever struggling to liberate itself from the bonds of even that flimsy prison; hence the “sons of God,” in their imprudent efforts,
were the first to trace a future model for the cyclic law But, man must not be “like one of us,” says the Creative Deity, one of the Elohim “intrusted with the fabrication of the lower animal.”[488] And thus it was, when the men of the first race had reached the summit of the first cycle, they lost their balance, and their second envelope, the grosser clothing (astral body), dragged them down the opposite arc.
This kabalistic version of the sons of God (or of light) is given in the Codex Nazaræus. Bahak-Zivo, the “father of genii, is ordered to ‘construct creatures.’” But, as he is “ignorant of Orcus,” he fails to do so and calls in Fetahil a still purer spirit to his aid, who fails still worse.
Then steps on the stage of creation the “spirit”[489] (which properly ought to be translated “soul,” for it is the anima mundi, and which with the Nazarenes and the Gnostics was feminine), and perceiving that for Fetahil,[490] the newest man (the latest), the splendor was “changed,” and that for splendor existed “decrease and damage,” awakes Karabtanos,[491] “who was frantic and without sense and judgment,” and says to him: “Arise; see, the splendor (light) of the newest man (Fetahil) has failed (to produce or create men), the decrease of this splendor is visible. Rise up, come with thy MOTHER (the spiritus) and free thee from limits by which thou art held, and those more ample than the whole world.” After which follows the union of the frantic and blind matter, guided by the insinuations of the spirit (not the Divine breath, but the Astral spirit, which by its double essence is already tainted with matter) and the offer of the mother being accepted the Spiritus conceives “Seven Figures,” which Irenæus is disposed to take for the seven stellars (planets) but which represent the seven capital sins, the progeny of an astral soul separated from its divine source (spirit) and matter, the blind demon of concupiscence. Seeing this, Fetahil extends his hand toward the abyss of matter, and says: ‘Let the earth exist, just as the abode of the powers has existed.’” Dipping his hand in the chaos, which he condenses, he creates our planet.[492]
Then the Codex proceeds to tell how Bahak-Zivo was separated from the Spiritus, and the genii, or angels, from the rebels.[493] Then Mano[494] (the greatest), who dwells with the greatest F , calls Kebar-Zivo (known also by the name of Nebat-Iavar bar Iufin-Ifafin), Helm and Vine of the food of life,[495] he being the third life, and, commiserating the rebellious and foolish genii, on account of the magnitude of their ambition, says: “Lord of the genii[496] (Æons), see what the genii, the rebellious angels do, and about what they are consulting.[497] They say, “Let us call forth the world, and let us call the ‘powers’ into existence. The genii are the Principes, the ‘sons of Light,’ but thou art the ‘Messenger of Life.’”[498]
And in order to counteract the influence of the seven “badly disposed” principles, the progeny of Spiritus, C Z , the mighty Lord of Splendor, procreates seven other lives (the cardinal virtues) who shine in their own form and light “from on high”[499] and thus reëstablishes the balance between good and evil, light and darkness.
But this creation of beings, without the requisite influx of divine pure breath in them, which was known among the kabalists as the “Living Fire,” produced but creatures of matter and astral light.[500] Thus were generated the animals which preceded man on this earth. The spiritual beings, the “sons of light,” those who remained faithful to the great Ferho (the First Cause of all), constitute the celestial or angelic hierarchy, the Adonim, and the legions of the neverembodied spiritual men. The followers of the rebellious and foolish genii, and the descendants of the “witless” seven spirits begotten by “Karabtanos” and the “spiritus,” became, in course of time, the “men of our planet,”[501] after having previously passed through every “creation” of every one of the elements. From this stage of life they have been traced by Darwin, who shows us how our highest forms have been evolved out of the lowest. Anthropology dares not follow the kabalist in his metaphysical flights beyond this planet, and it is doubtful if its teachers have the courage to search for the missing link in the old kabalistic manuscripts.
Thus was set in motion the first cycle, which in its rotations downward, brought an infinitesimal part of the created lives to our planet of mud. Arrived at the lowest point of the arc of the cycle which directly preceded life on this earth, the pure divine spark still lingering in the Adam made an effort to separate itself from the astral spirit, for “man was falling gradually into generation,” and the fleshy coat was becoming with every action more and more dense.
And now comes a mystery, a Sod;[502] a secret which Rabbi Simeon[503] imparted but to very few initiates. It was enacted once every seven years during the Mysteries of Samothrace, and the records of it are found self-printed on the leaves of the Thibetan sacred tree, the mysterious K , in the Lamasery of the holy adepts.[504]
In the shoreless ocean of space radiates the central, spiritual, and Invisible sun. The universe is his body, spirit and soul; and after this ideal model are framed all things. These three emanations are the three lives, the three degrees of the gnostic Pleroma, the three “Kabalistic Faces,” for the A of the ancient, the holy of the aged, the great En-Soph, “has a form and then he has no form.” The invisible “assumed a form when he called the universe into existence,”[505] says the Sohar, the Book of splendor. The first light is His soul, the Infinite, Boundless, and Immortal breath; under the efflux of which the universe heaves its mighty bosom, infusing Intelligent life throughout creation. The second emanation condenses cometary matter and produces forms within the cosmic circle; sets the countless worlds floating in the electric space, and infuses the unintelligent, blind life-principle into every form. The third, produces the whole universe of physical matter; and as it keeps gradually receding from the Central Divine Light its brightness wanes and it becomes D and the B —pure matter, the “gross purgations of the celestial fire” of the Hermetists.
When the Central Invisible (the Lord Ferho) saw the efforts of the divine Scintilla, unwilling to be dragged lower down into the degradation of matter, to liberate itself, he permitted it to shoot out
from itself a monad, over which, attached to it as by the finest thread, the Divine Scintilla (the soul) had to watch during its ceaseless peregrinations from one form to another. Thus the monad was shot down into the first form of matter and became encased in stone; then, in course of time, through the combined efforts of living fire and living water, both of which shone their reflection upon the stone, the monad crept out of its prison to sunlight as a lichen. From change to change it went higher and higher; the monad, with every new transformation borrowing more of the radiance of its parent, Scintilla, which approached it nearer at every transmigration. For “the First Cause, had willed it to proceed in this order;” and destined it to creep on higher until its physical form became once more the Adam of dust, shaped in the image of the Adam Kadmon. Before undergoing its last earthly transformation, the external covering of the monad, from the moment of its conception as an embryo, passes in turn, once more, through the phases of the several kingdoms. In its fluidic prison it assumes a vague resemblance at various periods of the gestation to plant, reptile, bird, and animal, until it becomes a human embryo.[506] At the birth of the future man, the monad, radiating with all the glory of its immortal parent which watches it from the seventh sphere, becomes senseless. [507] It loses all recollection of the past, and returns to consciousness but gradually, when the instinct of childhood gives way to reason and intelligence. After the separation between the life-principle (astral spirit) and the body takes place, the liberated soul—Monad, exultingly rejoins the mother and father spirit, the radiant Augoeides, and the two, merged into one, forever form, with a glory proportioned to the spiritual purity of the past earth-life, the Adam who has completed the circle of necessity, and is freed from the last vestige of his physical encasement. Henceforth, growing more and more radiant at each step of his upward progress, he mounts the shining path that ends at the point from which he started around the GRAND CYCLE.
The whole Darwinian theory of natural selection is included in the first six chapters of the book of Genesis. The “Man” of chapter i. is radically different from the “Adam” of chapter ii., for the former was created “male and female” that is, bi-sexed—and in the image of
God; while the latter, according to verse seven, was formed of the dust of the ground, and became “a living soul,” after the Lord God “breathed into his nostrils the breath of life.” Moreover, this Adam was a male being, and in verse twenty we are told that “there was not found a helpmeet for him.” The Adonai, being pure spiritual entities, had no sex, or rather had both sexes united in themselves, like their Creator; and the ancients understood this so well that they represented many of their deities as of dual sex. The Biblical student must either accept this interpretation, or make the passages in the two chapters alluded to absurdly contradict each other It was such literal acceptance of passages that warranted the atheists in covering the Mosaic account with ridicule, and it is the dead letter of the old text that begets the materialism of our age. Not only are these two races of beings thus clearly indicated in Genesis, but even a third and a fourth one are ushered before the reader in chapter iv., where the “sons of God” and the race of “giants” are spoken of.
As we write, there appears in an American paper, The Kansas City Times, an account of important discoveries of the remains of a prehistorical race of giants, which corroborates the statements of the kabalists and the Bible allegories at the same time. It is worth preserving:
“In his researches among the forests of Western Missouri, Judge E. P. West has discovered a number of conical-shaped mounds, similar in construction to those found in Ohio and Kentucky. These mounds are found upon the high bluffs overlooking the Missouri River, the largest and more prominent being found in Tennessee, Mississippi, and Louisiana. Until about three weeks ago it was not suspected that the mound builders had made this region their home in the prehistoric days; but now it is discovered that this strange and extinct race once occupied this land, and have left an extensive graveyard in a number of high mounds upon the Clay County bluffs.
“As yet, only one of these mounds has been opened. Judge West discovered a skeleton about two weeks ago, and made a report to other members of the society. They accompanied him to the mound, and not far from the surface excavated and took out the remains of
two skeletons. The bones are very large—so large, in fact, when compared with an ordinary skeleton of modern date, they appear to have formed part of a giant. The head bones, such as have not rotted away, are monstrous in size. The lower jaw of one skeleton is in a state of preservation, and is double the size of the jaw of a civilized person. The teeth in this jaw-bone are large, and appear to have been ground down and worn away by contact with roots and carnivorous food. The jaw-bone indicates immense muscular strength. The thigh-bone, when compared with that of an ordinary modern skeleton, looks like that of a horse. The length, thickness, and muscular development are remarkable. But the most peculiar part about the skeleton is the frontal bone. It is very low, and differs radically from any ever seen in this section before. It forms one thick ridge of bone about one inch wide, extending across the eyes. It is a narrow but rather heavy ridge of bone which, instead of extending upward, as it does now in these days of civilization, receded back from the eyebrows, forming a flat head, and thus indicates a very low order of mankind. It is the opinion of the scientific gentlemen who are making these discoveries that these bones are the remains of a prehistoric race of men. They do not resemble the present existing race of Indians, nor are the mounds constructed upon any pattern or model known to have been in use by any race of men now in existence in America. The bodies are discovered in a sitting posture in the mounds, and among the bones are found stone weapons, such as flint knives, flint scrapers, and all of them different in shape to the arrow-heads, war-hatchets, and other stone tools and weapons known to have been in use by the aboriginal Indians of this land when discovered by the whites. The gentlemen who have these curious bones in charge have deposited them with Dr. Foe, on Main street. It is their intention to make further and closer researches in the mounds on the bluffs opposite this city. They will make a report of their labors at the next meeting of the Academy of Science, by which time they expect to be able to make some definite report as to their opinions. It is pretty definitely settled, however, that the skeletons are those of a race of men not now in existence.”
